TWI579888B - Mass spectrometer, the use thereof, and methods for mass spectrometric analysis of gas mixtures - Google Patents
Mass spectrometer, the use thereof, and methods for mass spectrometric analysis of gas mixtures Download PDFInfo
- Publication number
- TWI579888B TWI579888B TW103105973A TW103105973A TWI579888B TW I579888 B TWI579888 B TW I579888B TW 103105973 A TW103105973 A TW 103105973A TW 103105973 A TW103105973 A TW 103105973A TW I579888 B TWI579888 B TW I579888B
- Authority
- TW
- Taiwan
- Prior art keywords
- gas
- mass spectrometer
- ion trap
- ionized
- mass
- Prior art date
Links
- 239000000203 mixture Substances 0.000 title claims description 160
- 238000000034 method Methods 0.000 title claims description 89
- 238000004949 mass spectrometry Methods 0.000 title claims description 27
- 239000007789 gas Substances 0.000 claims description 433
- 150000002500 ions Chemical class 0.000 claims description 199
- 238000005040 ion trap Methods 0.000 claims description 193
- 239000002245 particle Substances 0.000 claims description 127
- 238000005259 measurement Methods 0.000 claims description 94
- 230000008569 process Effects 0.000 claims description 65
- 238000001900 extreme ultraviolet lithography Methods 0.000 claims description 30
- 238000001228 spectrum Methods 0.000 claims description 30
- 230000005284 excitation Effects 0.000 claims description 29
- 238000001514 detection method Methods 0.000 claims description 27
- 239000000126 substance Substances 0.000 claims description 27
- 238000004252 FT/ICR mass spectrometry Methods 0.000 claims description 25
- 230000005855 radiation Effects 0.000 claims description 25
- 238000004458 analytical method Methods 0.000 claims description 24
- 238000000576 coating method Methods 0.000 claims description 23
- 238000001819 mass spectrum Methods 0.000 claims description 18
- 238000005286 illumination Methods 0.000 claims description 17
- 239000011248 coating agent Substances 0.000 claims description 14
- 229910052734 helium Inorganic materials 0.000 claims description 14
- 238000010894 electron beam technology Methods 0.000 claims description 13
- 230000009467 reduction Effects 0.000 claims description 12
- 150000001875 compounds Chemical class 0.000 claims description 10
- 238000012937 correction Methods 0.000 claims description 10
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 claims description 9
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 9
- 238000004868 gas analysis Methods 0.000 claims description 8
- 239000001307 helium Substances 0.000 claims description 8
- 229910052787 antimony Inorganic materials 0.000 claims description 7
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims description 7
- 238000000231 atomic layer deposition Methods 0.000 claims description 7
- 238000001311 chemical methods and process Methods 0.000 claims description 7
- 239000007795 chemical reaction product Substances 0.000 claims description 7
- 229910052760 oxygen Inorganic materials 0.000 claims description 7
- 238000012545 processing Methods 0.000 claims description 7
- 238000003860 storage Methods 0.000 claims description 7
- SIJSIIFAIYLAQW-UHFFFAOYSA-N 1-tert-butyl-9h-fluorene Chemical compound C12=CC=CC=C2CC2=C1C=CC=C2C(C)(C)C SIJSIIFAIYLAQW-UHFFFAOYSA-N 0.000 claims description 6
- 229910052796 boron Inorganic materials 0.000 claims description 6
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims description 6
- 229910052799 carbon Inorganic materials 0.000 claims description 5
- 239000001257 hydrogen Substances 0.000 claims description 5
- 238000002488 metal-organic chemical vapour deposition Methods 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- 238000005240 physical vapour deposition Methods 0.000 claims description 5
- 238000011144 upstream manufacturing Methods 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- -1 CH 4 Inorganic materials 0.000 claims description 4
- 230000000694 effects Effects 0.000 claims description 4
- 238000012986 modification Methods 0.000 claims description 4
- 230000004048 modification Effects 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- 238000004812 paul trap Methods 0.000 claims description 4
- 238000002360 preparation method Methods 0.000 claims description 4
- NIIPNAJXERMYOG-UHFFFAOYSA-N 1,1,2-trimethylhydrazine Chemical compound CNN(C)C NIIPNAJXERMYOG-UHFFFAOYSA-N 0.000 claims description 3
- DIIIISSCIXVANO-UHFFFAOYSA-N 1,2-Dimethylhydrazine Chemical compound CNNC DIIIISSCIXVANO-UHFFFAOYSA-N 0.000 claims description 3
- YTPFRRRNIYVFFE-UHFFFAOYSA-N 2,2,3,3,5,5-hexamethyl-1,4-dioxane Chemical compound CC1(C)COC(C)(C)C(C)(C)O1 YTPFRRRNIYVFFE-UHFFFAOYSA-N 0.000 claims description 3
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 3
- QFGYDGCFIGCDAG-UHFFFAOYSA-N CCC1=CC2=C(CC3=CC=CC=C32)C(=C1CC)C(C)(C)C Chemical compound CCC1=CC2=C(CC3=CC=CC=C32)C(=C1CC)C(C)(C)C QFGYDGCFIGCDAG-UHFFFAOYSA-N 0.000 claims description 3
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 claims description 3
- 229910052782 aluminium Inorganic materials 0.000 claims description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 3
- 229910052785 arsenic Inorganic materials 0.000 claims description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 3
- SLLGVCUQYRMELA-UHFFFAOYSA-N chlorosilicon Chemical compound Cl[Si] SLLGVCUQYRMELA-UHFFFAOYSA-N 0.000 claims description 3
- CRHWEIDCXNDTMO-UHFFFAOYSA-N ditert-butylphosphane Chemical compound CC(C)(C)PC(C)(C)C CRHWEIDCXNDTMO-UHFFFAOYSA-N 0.000 claims description 3
- 238000005530 etching Methods 0.000 claims description 3
- 229910052733 gallium Inorganic materials 0.000 claims description 3
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 3
- 229910052737 gold Inorganic materials 0.000 claims description 3
- 239000010931 gold Substances 0.000 claims description 3
- 238000002513 implantation Methods 0.000 claims description 3
- 229910052738 indium Inorganic materials 0.000 claims description 3
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims description 3
- 239000001301 oxygen Substances 0.000 claims description 3
- 229910052698 phosphorus Inorganic materials 0.000 claims description 3
- 238000000623 plasma-assisted chemical vapour deposition Methods 0.000 claims description 3
- FTXVBUWNYOLMMQ-UHFFFAOYSA-N tert-butyl(diethyl)phosphane Chemical compound CCP(CC)C(C)(C)C FTXVBUWNYOLMMQ-UHFFFAOYSA-N 0.000 claims description 3
- DZLFLBLQUQXARW-UHFFFAOYSA-N tetrabutylammonium Chemical compound CCCC[N+](CCCC)(CCCC)CCCC DZLFLBLQUQXARW-UHFFFAOYSA-N 0.000 claims description 3
- VOITXYVAKOUIBA-UHFFFAOYSA-N triethylaluminium Chemical compound CC[Al](CC)CC VOITXYVAKOUIBA-UHFFFAOYSA-N 0.000 claims description 3
- OTRPZROOJRIMKW-UHFFFAOYSA-N triethylindigane Chemical compound CC[In](CC)CC OTRPZROOJRIMKW-UHFFFAOYSA-N 0.000 claims description 3
- JLTRXTDYQLMHGR-UHFFFAOYSA-N trimethylaluminium Chemical compound C[Al](C)C JLTRXTDYQLMHGR-UHFFFAOYSA-N 0.000 claims description 3
- XCZXGTMEAKBVPV-UHFFFAOYSA-N trimethylgallium Chemical compound C[Ga](C)C XCZXGTMEAKBVPV-UHFFFAOYSA-N 0.000 claims description 3
- IBEFSUTVZWZJEL-UHFFFAOYSA-N trimethylindium Chemical compound C[In](C)C IBEFSUTVZWZJEL-UHFFFAOYSA-N 0.000 claims description 3
- BSJHUPBWYHUCDB-UHFFFAOYSA-N C(CCC)C(C(CCCC)(CCCC)CCCC)CCCCCCCC Chemical compound C(CCC)C(C(CCCC)(CCCC)CCCC)CCCCCCCC BSJHUPBWYHUCDB-UHFFFAOYSA-N 0.000 claims description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
- 229910052797 bismuth Inorganic materials 0.000 claims description 2
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims description 2
- 239000003344 environmental pollutant Substances 0.000 claims description 2
- 238000004150 penning trap Methods 0.000 claims description 2
- 231100000719 pollutant Toxicity 0.000 claims description 2
- 238000003556 assay Methods 0.000 claims 1
- BLJHFCVPKWOHJX-UHFFFAOYSA-N ethylgallium Chemical compound CC[Ga] BLJHFCVPKWOHJX-UHFFFAOYSA-N 0.000 claims 1
- 230000003287 optical effect Effects 0.000 description 15
- 238000011161 development Methods 0.000 description 13
- 238000004140 cleaning Methods 0.000 description 12
- 239000000356 contaminant Substances 0.000 description 10
- 239000002243 precursor Substances 0.000 description 10
- 238000010926 purge Methods 0.000 description 10
- 238000009825 accumulation Methods 0.000 description 9
- 230000033001 locomotion Effects 0.000 description 8
- 229910052751 metal Inorganic materials 0.000 description 8
- 239000002184 metal Substances 0.000 description 8
- 230000007935 neutral effect Effects 0.000 description 8
- 239000000758 substrate Substances 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 7
- 239000012491 analyte Substances 0.000 description 6
- 230000005684 electric field Effects 0.000 description 6
- 239000012159 carrier gas Substances 0.000 description 5
- 238000010348 incorporation Methods 0.000 description 5
- 238000000691 measurement method Methods 0.000 description 5
- 230000036961 partial effect Effects 0.000 description 5
- 230000004044 response Effects 0.000 description 5
- 230000003595 spectral effect Effects 0.000 description 5
- 230000036962 time dependent Effects 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- 229910052786 argon Inorganic materials 0.000 description 4
- 238000012512 characterization method Methods 0.000 description 4
- 238000005229 chemical vapour deposition Methods 0.000 description 4
- 238000011065 in-situ storage Methods 0.000 description 4
- 238000012544 monitoring process Methods 0.000 description 4
- 238000004321 preservation Methods 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- 230000001360 synchronised effect Effects 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 230000007423 decrease Effects 0.000 description 3
- 238000013461 design Methods 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 239000002019 doping agent Substances 0.000 description 3
- NPEOKFBCHNGLJD-UHFFFAOYSA-N ethyl(methyl)azanide;hafnium(4+) Chemical compound [Hf+4].CC[N-]C.CC[N-]C.CC[N-]C.CC[N-]C NPEOKFBCHNGLJD-UHFFFAOYSA-N 0.000 description 3
- 239000012634 fragment Substances 0.000 description 3
- 238000013467 fragmentation Methods 0.000 description 3
- 238000006062 fragmentation reaction Methods 0.000 description 3
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 3
- 238000009434 installation Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
- 239000000376 reactant Substances 0.000 description 3
- 125000004429 atom Chemical group 0.000 description 2
- 230000004888 barrier function Effects 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 238000011109 contamination Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 230000001419 dependent effect Effects 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 238000005137 deposition process Methods 0.000 description 2
- 239000013067 intermediate product Substances 0.000 description 2
- 229910052743 krypton Inorganic materials 0.000 description 2
- 238000001459 lithography Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000005334 plasma enhanced chemical vapour deposition Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 230000035945 sensitivity Effects 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 230000001052 transient effect Effects 0.000 description 2
- RGGPNXQUMRMPRA-UHFFFAOYSA-N triethylgallium Chemical compound CC[Ga](CC)CC RGGPNXQUMRMPRA-UHFFFAOYSA-N 0.000 description 2
- 229910052724 xenon Inorganic materials 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- WWBNKPXDLFYQEE-UHFFFAOYSA-N CCCCCCCC(CCCC)C(CCCC)(CCCC)CCCC Chemical compound CCCCCCCC(CCCC)C(CCCC)(CCCC)CCCC WWBNKPXDLFYQEE-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 210000001124 body fluid Anatomy 0.000 description 1
- 239000010839 body fluid Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 230000003750 conditioning effect Effects 0.000 description 1
- 238000013016 damping Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000005672 electromagnetic field Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000000407 epitaxy Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 1
- CJNBYAVZURUTKZ-UHFFFAOYSA-N hafnium(iv) oxide Chemical compound O=[Hf]=O CJNBYAVZURUTKZ-UHFFFAOYSA-N 0.000 description 1
- 238000012625 in-situ measurement Methods 0.000 description 1
- 238000001802 infusion Methods 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000000534 ion trap mass spectrometry Methods 0.000 description 1
- 238000010884 ion-beam technique Methods 0.000 description 1
- 230000002045 lasting effect Effects 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 238000001451 molecular beam epitaxy Methods 0.000 description 1
- NJPPVKZQTLUDBO-UHFFFAOYSA-N novaluron Chemical compound C1=C(Cl)C(OC(F)(F)C(OC(F)(F)F)F)=CC=C1NC(=O)NC(=O)C1=C(F)C=CC=C1F NJPPVKZQTLUDBO-UHFFFAOYSA-N 0.000 description 1
- 210000000056 organ Anatomy 0.000 description 1
- 230000010355 oscillation Effects 0.000 description 1
- SIWVEOZUMHYXCS-UHFFFAOYSA-N oxo(oxoyttriooxy)yttrium Chemical compound O=[Y]O[Y]=O SIWVEOZUMHYXCS-UHFFFAOYSA-N 0.000 description 1
- 238000004886 process control Methods 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 238000004445 quantitative analysis Methods 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 235000013619 trace mineral Nutrition 0.000 description 1
- 239000011573 trace mineral Substances 0.000 description 1
- 238000000927 vapour-phase epitaxy Methods 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
- H01J49/00—Particle spectrometers or separator tubes
- H01J49/02—Details
- H01J49/04—Arrangements for introducing or extracting samples to be analysed, e.g. vacuum locks; Arrangements for external adjustment of electron- or ion-optical components
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
- H01J49/00—Particle spectrometers or separator tubes
- H01J49/02—Details
- H01J49/10—Ion sources; Ion guns
- H01J49/14—Ion sources; Ion guns using particle bombardment, e.g. ionisation chambers
- H01J49/145—Ion sources; Ion guns using particle bombardment, e.g. ionisation chambers using chemical ionisation
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
- H01J49/00—Particle spectrometers or separator tubes
- H01J49/0027—Methods for using particle spectrometers
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
- H01J49/00—Particle spectrometers or separator tubes
- H01J49/02—Details
- H01J49/10—Ion sources; Ion guns
- H01J49/105—Ion sources; Ion guns using high-frequency excitation, e.g. microwave excitation, Inductively Coupled Plasma [ICP]
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
- H01J49/00—Particle spectrometers or separator tubes
- H01J49/02—Details
- H01J49/10—Ion sources; Ion guns
- H01J49/14—Ion sources; Ion guns using particle bombardment, e.g. ionisation chambers
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
- H01J49/00—Particle spectrometers or separator tubes
- H01J49/02—Details
- H01J49/10—Ion sources; Ion guns
- H01J49/14—Ion sources; Ion guns using particle bombardment, e.g. ionisation chambers
- H01J49/147—Ion sources; Ion guns using particle bombardment, e.g. ionisation chambers with electrons, e.g. electron impact ionisation, electron attachment
Landscapes
- Chemical & Material Sciences (AREA)
- Analytical Chemistry (AREA)
- Physics & Mathematics (AREA)
- Engineering & Computer Science (AREA)
- Plasma & Fusion (AREA)
- Other Investigation Or Analysis Of Materials By Electrical Means (AREA)
- Electron Tubes For Measurement (AREA)
- Drying Of Semiconductors (AREA)
Description
本發明係關於一種用於氣體混合物之質譜分析的質譜儀，包含：離子化裝置及用於氣體混合物之保存和質譜分析的離子阱。本發明還有關這種質譜儀的用途及氣體混合物的質譜分析方法。 The present invention relates to a mass spectrometer for mass spectrometry of a gas mixture, comprising: an ionization device and an ion trap for storage and mass spectrometry of the gas mixture. The invention also relates to the use of such mass spectrometers and mass spectrometric methods of gas mixtures.
用於分析EUV微影設備中的殘餘氣體並具有用於保存至少一種污染物質的離子阱的質譜儀可從WO 2010/022815 A1得知。 A mass spectrometer for the analysis of residual gases in an EUV lithography apparatus and having an ion trap for the preservation of at least one contaminant is known from WO 2010/022815 A1.
質譜儀不僅被用於EUV微影術，而且還被用在許多其它的領域中，例如在醫療化學中特徵化化合物、在法醫檢驗中鑑別體液或器官中的物質、化學武器的添加劑檢測或軍事分析等。質譜儀也可用於藥物動力學和真空技術中的殘餘氣體分析。 Mass spectrometers are not only used in EUV lithography, but are also used in many other fields, such as characterization of compounds in medical chemistry, identification of substances in body fluids or organs in forensic testing, additive testing of chemical weapons, or military Analysis and so on. Mass spectrometers are also available for residual gas analysis in pharmacokinetic and vacuum technologies.
在氣態物質或氣體混合物的質譜分析中，測定原子或分子的質量(更確切來說為質荷比)以獲得氣態物質的化學特性。待分析的物質或待分析的物質混合物不是已經存在氣相中就是被轉化為氣相，以藉由離子化單元進行離子化。在傳統的質譜儀中，以這種方式離子化的物質被供應到分析器，而且通常被導引通過電場及/或磁場，其中離子由於不同的荷 質比而畫出特徵軌道，因此得以區別該等離子。 In mass spectrometry of a gaseous substance or gas mixture, the mass of the atom or molecule (more precisely, the mass to charge ratio) is determined to obtain the chemical properties of the gaseous substance. The substance to be analyzed or the substance mixture to be analyzed is either already present in the gas phase or converted into a gas phase for ionization by means of an ionization unit. In conventional mass spectrometers, substances ionized in this manner are supplied to the analyzer and are typically directed through an electric field and/or a magnetic field, where the ions are due to different charges. The characteristic orbit is drawn in order to distinguish the plasma.
由於目前可取得質譜儀的缺點，例如尺寸大、掃描量測緩慢、沒有特別高的靈敏度等，依據現有技術的質譜儀只能被使用於有限的範圍內，或甚至在許多應用中根本沒有運用。 Since the disadvantages of mass spectrometers are currently available, such as large size, slow scanning measurement, and no particularly high sensitivity, mass spectrometers according to the prior art can only be used in a limited range, or even in many applications. .
舉例來說明，來自氣體分析儀或質譜儀的量測訊號之穩定性在很大程度上是取決於離子化的短暫穩定性。傳統的四極質譜儀通常使用熱燈絲離子化來操作，而且通常具有約10%-20%的誤差。替代類型的離子化，例如同樣可用於質譜術的電漿離子化，由於電漿氣體調節及/或電漿功率波動中的不精確，通常具有在5%-10%範圍中的誤差。 By way of example, the stability of the measurement signal from a gas analyzer or mass spectrometer is largely dependent on the transient stability of the ionization. Conventional quadrupole mass spectrometers typically operate using hot filament ionization and typically have an error of between about 10% and 20%. Alternative types of ionization, such as plasma ionization, which are also useful for mass spectrometry, typically have an error in the range of 5%-10% due to inaccuracies in plasma gas conditioning and/or plasma power fluctuations.
在離子化期間與時間相關的波動導致量測訊號中有成比例的變化，從而使得量測承受相應的誤差。假使氣體分析儀或質譜儀打算在半導體業或化學業中被用於定量量測及/或監測及/或分析氣相製程，則此誤差是特別不利的。 The time-dependent fluctuations during ionization result in a proportional change in the measurement signal, so that the measurement is subject to the corresponding error. This error is particularly disadvantageous if the gas analyzer or mass spectrometer is intended to be used in the semiconductor industry or in the chemical industry for quantitative measurement and/or monitoring and/or analysis of gas phase processes.
此外，在許多傳統質譜儀(例如四極質譜儀)的量測期間，連續掃描質量導致長的量測時間，在高解析度量測的情況下，長的量測時間會是在許多分鐘的範圍中，甚至是在多個小時的範圍中。 In addition, continuous scanning quality results in long measurement times during the measurement of many conventional mass spectrometers (such as quadrupole mass spectrometers). In the case of high resolution measurements, long measurement times can be in the range of many minutes. Medium, even in the range of multiple hours.
為了能夠檢測少量的分析物(即待檢測的氣體組分)，在高壓下的殘餘氣體或製程氣體中需要有大的動態範圍。一般來說，傳統的質譜儀只能有約106到至多107的動態範圍(最大可測訊號對最小可測訊號的比值)。 In order to be able to detect small amounts of analyte (ie the gas component to be detected), a large dynamic range is required in the residual gas or process gas at high pressure. In general, conventional mass spectrometers can only have a dynamic range of about 10 6 up to 10 7 (the ratio of the maximum measurable signal to the minimum measurable signal).
為了檢測殘餘氣體中的少量分析物，質譜儀需要具有非常低的檢測限制。目前可得的質譜儀可實現10-13毫巴至10-14毫巴的檢測限制。 對於敏感性檢測往往會使用電荷倍增器，電荷倍增器具有超過20%的大量散射，此外通常不能在相對高壓(>10-4毫巴)下使用。 In order to detect small amounts of analyte in the residual gas, the mass spectrometer needs to have very low detection limits. Currently available mass spectrometers can achieve detection limits of 10 -13 mbar to 10 -14 mbar. For sensitivity detection, a charge multiplier is often used, the charge multiplier has a large amount of scattering of more than 20%, and in addition it is generally not used at relatively high pressures (>10 -4 mbar).
此外，質譜儀被用於具有不同壓力範圍的分析物及/或背景氣體的不同應用情況。商業質譜儀通常被設計用於一個壓力範圍或另一個壓力範圍，但沒有質譜儀是在不使用為此目的而必須進行的複雜特定壓力重組下可以涵蓋非常大的壓力範圍的。 In addition, mass spectrometers are used for different applications of analytes and/or background gases with different pressure ranges. Commercial mass spectrometers are typically designed for one pressure range or another, but no mass spectrometer can cover a very large pressure range without the complex specific pressure recombination that must be performed for this purpose.
本發明之目的係提供一種質譜儀及一種簡化氣體或氣體混合物之分析的方法，特別是一種克服至少一個在開始時闡述的缺點的方法，使得質譜儀也可被用於迄今還不可能有這種用途或在很大困難下才有可能的應用領域中。 It is an object of the present invention to provide a mass spectrometer and a method for simplifying the analysis of a gas or gas mixture, in particular a method of overcoming at least one of the disadvantages set forth at the outset, such that the mass spectrometer can also be used to date. A kind of application or an application field that is possible under great difficulty.
依據本發明之第一態樣，此目的係藉由在開端闡述的類型的質譜儀來實現，其中該離子化裝置被體現用於供應離子化氣體之離子及/或介穩態粒子及/或用於供應電子至該離子阱，用以離子化待分析之該氣體混合物，其中該質譜儀(或其中設置的控制裝置)被體現或程式化來在分析該氣體混合物之前測定存在於該離子阱中的該離子化氣體之離子及/或介穩態粒子之數量及/或存在於該離子阱中的殘餘氣體之離子的數量。 According to a first aspect of the invention, the object is achieved by a mass spectrometer of the type set forth at the outset, wherein the ionization device is embodied for supplying ions and/or metastable particles of the ionized gas and/or Providing electrons to the ion trap for ionizing the gas mixture to be analyzed, wherein the mass spectrometer (or a control device disposed therein) is embodied or programmed to determine presence in the ion trap prior to analyzing the gas mixture The number of ions and/or metastable particles of the ionized gas and/or the number of ions of residual gas present in the ion trap.
依據本發明之此態樣，提出在量測單元中離子化該氣體混合物，該量測單元可以被體現為離子阱或可以含有離子阱。在此情況下，待 分析的該氣體混合物通常在非離子化狀態下被以氣流或氣體脈衝的形式供應到該離子阱或該量測單元，而且該離子化較佳係直接在該離子阱中(原位)進行；確切來說，在典型的方式中，藉由使用該離子化氣體之離子及/或介穩態粒子或使用該等電子來碰撞離子化或電荷交換離子化該氣體混合物。該離子化可以選擇性地在該離子阱外之量測室中進行。在此案例中，該離子化較佳在直接鄰近該離子阱處進行，並且該離子化氣體混合物之離子被輸入該離子阱中。 According to this aspect of the invention, it is proposed to ionize the gas mixture in a measuring unit, which may be embodied as an ion trap or may contain an ion trap. In this case, wait The analyzed gas mixture is typically supplied to the ion trap or the measuring unit in the form of a gas stream or a gas pulse in a non-ionized state, and the ionization is preferably performed directly in the ion trap (in situ); Specifically, in a typical manner, the gas mixture is ionized by ionization or charge exchange by using ions and/or metastable particles of the ionized gas or using the electrons. The ionization can be selectively performed in a measurement chamber outside the ion trap. In this case, the ionization is preferably performed directly adjacent to the ion trap, and ions of the ionized gas mixture are introduced into the ion trap.
此處，用於供應待分析的該氣體混合物進入該離子阱的入口可以被設置在與用於供應該離子化氣體之該離子及/或該介穩態粒子或該等電子的入口相對，使得供應的氣體混合物之氣流和來自該離子化氣體之離子或介穩態粒子及/或該等電子的粒子束被對齊面向彼此並在該離子阱中或視情況在直接鄰近該離子阱處互相碰撞。 Here, an inlet for supplying the gas mixture to be analyzed into the ion trap may be disposed opposite to an inlet for supplying the ionized gas and/or the metastable particle or the electrons, such that The gas stream of the supplied gas mixture and the ion or metastable particles from the ionized gas and/or the beam of the electrons are aligned to face each other and collide with each other in the ion trap or, as appropriate, directly adjacent to the ion trap .
如上面進一步描述，待分析的氣體混合物可以被電子、離子化氣體之離子及/或離子化氣體之介穩態粒子離子化。介穩態粒子被理解為意指離子化氣體之原子或分子，該原子或分子為電中性的但處於激發(高能)電子態。在本案例中，待分析的氣體混合物係被理解為意指氣態物質之混合物，該氣態物質之混合物可以視情況地還包含粒子，即該氣態物質具有>100amu、視情況地>1000amu或>10000amu、甚至高達2000000的質量數(amu-原子質量單位(atomic mass unit))，即該粒子可具有巨分子結構且具有約0.001μm-10μm或更大的粒度。 As further described above, the gas mixture to be analyzed can be ionized by electrons, ions of ionized gas, and/or metastable particles of ionized gas. Metastable particles are understood to mean atoms or molecules of an ionizing gas that are electrically neutral but in an excited (high energy) electronic state. In the present case, the gas mixture to be analyzed is understood to mean a mixture of gaseous substances, which may optionally also comprise particles, ie the gaseous substance has >100 amu, optionally >1000 amu or >10000 amu Even a mass number of 2,000,000 (amu-atomic mass unit), that is, the particles may have a macromolecular structure and have a particle size of about 0.001 μm to 10 μm or more.
典型地，諸如保羅離子阱(Paul ion trap)的3D離子阱被用來作為質譜儀的離子阱；此處，待分析的氣態組分或待分析的氣體混合物 陷於全部三個空間尺寸中，使得後者在全部三個空間尺寸中進行穩定的振盪，並因此可用於相對長時間(通常1ms或更久，較佳短於1秒或100ms)的量測。離子化氣態組分陷入的空間之尺寸通常為小於50cm x 50cm x 50cm，較佳為小於50mm x 50mm x 50mm。 Typically, a 3D ion trap such as the Paul ion trap is used as the ion trap of the mass spectrometer; here, the gaseous component to be analyzed or the gas mixture to be analyzed Being trapped in all three spatial dimensions allows the latter to oscillate stably in all three spatial dimensions and can therefore be used for measurements over relatively long periods of time (typically 1 ms or longer, preferably shorter than 1 second or 100 ms). The size of the space into which the ionized gaseous component is trapped is typically less than 50 cm x 50 cm x 50 cm, preferably less than 50 mm x 50 mm x 50 mm.
該質譜儀較佳具有可控入口，用於脈衝式供應待分析之該氣體混合物至該離子阱，而且該質譜儀被體現或程式化來考量該離子化氣體的離子及/或介穩態粒子之測得數量及/或該殘餘氣體的離子之測得數量而測定在該質譜儀中的離子化氣體混合物之待分析組分或離子群體之粒子數。離子化氣體之主離子(即離子化氣體和殘餘氣體之離子)或介穩態粒子之測得數量用以在量測或檢測期間進行校正，以最小化時間相關的波動對提供用於離子化的離子化氣體之主離子或介穩態粒子之數量或殘餘氣體之離子數量的影響。在脈衝式操作離子阱的情況下，為達此目的可以在供應各別氣體脈衝之前憑藉離子及/或介穩態粒子之測得數量進行校正，離子及/或介穩態粒子之測得數量可用於離子化該氣體混合物之各別氣體脈衝，並在測定待分析的該氣體混合物之氣體脈衝之待分析的離子化組分之粒子數量時被考量。舉例來說，離子或介穩態粒子之測得數量可以在藉由將該數量涵括在比例常數(校正因子)中來測定粒子數時被考量，藉由該比例常數乘以量測結果(即量測訊號位準)以校正待分析的氣體混合物之離子化組分的測得粒子數。 Preferably, the mass spectrometer has a controllable inlet for pulsing supply of the gas mixture to be analyzed to the ion trap, and the mass spectrometer is embodied or programmed to consider ion and/or metastable particles of the ionized gas The measured number and/or the measured amount of ions of the residual gas determine the number of particles of the component or ionic population to be analyzed of the ionized gas mixture in the mass spectrometer. The measured amount of the primary ion of the ionized gas (ie, the ionized gas and residual gas ions) or metastable particles is used to correct during measurement or detection to minimize time-dependent fluctuations provided for ionization The number of primary ions or metastable particles of the ionized gas or the number of ions of the residual gas. In the case of a pulsed operated ion trap, this can be corrected for the number of ions and/or metastable particles measured before the individual gas pulses are supplied, and the number of ions and/or metastable particles measured. The individual gas pulses that can be used to ionize the gas mixture are taken into account when determining the number of particles of the ionized component to be analyzed for the gas pulse of the gas mixture to be analyzed. For example, the measured amount of ion or metastable particles can be considered by determining the number of particles by including the quantity in a proportionality constant (correction factor), by multiplying the proportional constant by the measurement result ( That is, the signal level is measured to correct the measured number of particles of the ionized component of the gas mixture to be analyzed.
一般來說，該離子阱經由可控入口(例如可控閥形式的)被連接到腔室(例如處理室)，在該腔室中含有待分析的氣體混合物。該可控入口與該離子阱之操作同步，該離子阱通常被體現為ETIT(傅立葉轉換離 子阱)。因此，該離子化裝置還可以具有特別是用於脈衝式供應離子化氣體之離子或介穩態粒子及/或電子的可控入口。 Generally, the ion trap is connected to a chamber (e.g., a processing chamber) via a controllable inlet (e.g., in the form of a controllable valve) containing a gas mixture to be analyzed. The controllable inlet is synchronized with the operation of the ion trap, which is typically embodied as ETIT (Fourier Transform Deviation) Sub-trap). Thus, the ionization device can also have a controllable inlet for ion or metastable particles and/or electrons, in particular for the pulsed supply of ionized gas.
為了檢測待分析的氣體混合物，電子或該離子化氣體之離子及/或介穩態粒子最初被射入離子阱中，且該離子阱中通常存在離子化之殘餘氣體。產生的殘餘氣體離子及該離子化氣體之離子(以下一起被指稱為主離子)被陷在或保存在離子阱中。該主離子現在被交流電訊號激發，使得該主離子進行密閉的三維移動(雲霄飛車式移動)。該雲霄飛車式移動在該離子阱之覆蓋電極或量測電極上誘發圖像電流，從該圖像電流之大小可以以小於5%的精確度測定該離子阱中的主離子數量。在本申請案的意義內，主離子的數量也被理解為意指與主離子的數量成比例的值。 In order to detect the gas mixture to be analyzed, electrons or ions of the ionized gas and/or metastable particles are initially injected into the ion trap, and ionized residual gas is usually present in the ion trap. The generated residual gas ions and ions of the ionized gas (hereinafter collectively referred to as main ions) are trapped or held in the ion trap. The main ion is now excited by the alternating current signal, causing the main ion to perform a closed three-dimensional movement (cloud-moving movement). The roller coaster motion induces an image current on a cover electrode or a measurement electrode of the ion trap, and the magnitude of the current of the image can be used to determine the number of primary ions in the ion trap with an accuracy of less than 5%. Within the meaning of the present application, the number of primary ions is also understood to mean a value proportional to the number of primary ions.
替代地或另外地，還可以測定該離子阱中該離子化氣體之(中性)介穩態粒子的數量，例如藉由測定該離子阱中的普遍壓力，如藉由離子瞬態(即量測電極上的圖像電流)的時間縮短(時間常數)，因為此係直接與平均自由路徑長度相關並因此與壓力相關。該離子阱中的壓力基本上是由為了離子化的目地被引入該離子阱的離子化氣體(例如氦)所測定的，使得由此可以測定存在於該離子阱中的介穩態粒子之實際數量，因為該離子化氣體之離子數同樣可以藉由圖像電流的大小來測定(參見以上)。假使離子化氣體主要由介穩態粒子所組成，則還可以視情況地省略測定離子化氣體之離子數(反之亦然)。在此情況下由於殘餘氣體(例如水)的壓力通常明顯較低(一般約3-4個量級)，故可以忽略殘餘氣體中的介穩態粒子數量。另外用於測定介穩態粒子之數量的選擇係由測定位於該離子阱中的殘餘氣體(例如水)之粒子數量所組成，該殘餘氣體係被該離子化 氣體之介穩態粒子離子化，以由此間接測定已使該殘餘氣體離子化的介穩態粒子之數量。 Alternatively or additionally, the number of (neutral) metastable particles of the ionized gas in the ion trap can also be determined, for example by measuring the general pressure in the ion trap, such as by ion transients (ie, by amount) The time of the image current on the measuring electrode is shortened (time constant) since this is directly related to the mean free path length and therefore to the pressure. The pressure in the ion trap is substantially determined by the ionization gas (e.g., helium) introduced into the ion trap for the purpose of ionization, thereby making it possible to determine the actual amount of metastable particles present in the ion trap. The number, because the number of ions of the ionized gas can also be determined by the magnitude of the image current (see above). If the ionized gas is mainly composed of metastable particles, the number of ions for measuring the ionized gas may also be omitted as appropriate (and vice versa). In this case, since the pressure of the residual gas (e.g., water) is usually significantly lower (generally about 3-4 orders of magnitude), the amount of metastable particles in the residual gas can be ignored. Further, the selection for determining the amount of metastable particles consists of determining the number of particles of residual gas (e.g., water) located in the ion trap, and the residual gas system is ionized. The metastable particles of the gas are ionized to thereby indirectly determine the amount of metastable particles that have ionized the residual gas.
如此說來，以上述的方式，可以測定在該離子阱的氣體混合物的後續分析期間的背景雜訊。量測背景雜訊之後，打開可控氣體入口並將待分析氣體或氣體混合物從腔室以氣體脈衝的形式引入量測室(或引入離子阱)。氣體脈衝通過離子阱中的開口進入離子阱，並在離子阱中經由電荷交換處理或藉由碰撞離子化被電子及/或主離子或介穩態粒子離子化，並保持陷入該離子阱中用於質譜分析。 In this way, background noise during subsequent analysis of the gas mixture of the ion trap can be determined in the manner described above. After measuring the background noise, the controllable gas inlet is opened and the gas or gas mixture to be analyzed is introduced into the measurement chamber (or introduced into the ion trap) from the chamber in the form of a gas pulse. The gas pulse enters the ion trap through an opening in the ion trap and is ionized by the charge exchange process or by collision ionization by electrons and/or main ions or metastable particles, and remains trapped in the ion trap. For mass spectrometry analysis.
待分析的氣體混合物離子化之後，待分析的氣體混合物之離子或離子化組分被電脈衝訊號(激發訊號)激發。在過程中，待分析的氣體混合物之離子被帶入雲霄飛車式移動，其中每個質荷比(m/z)具有不同的雲霄飛車式頻率。如同在主離子的情況，這些雲霄飛車式移動在覆蓋電極或量測電極上產生圖像電流。可以對此被指配給離子的量測訊號施加傅立葉轉換，其中每個傅立葉頻率可以被指配到一個質荷比m/z，而且在相應的質荷比m/z下，被指配到每個頻率的訊號位準(Hf)係與待分析離子化組分之各別離子群體的離子數或粒子數成正比。 After ionization of the gas mixture to be analyzed, the ion or ionization component of the gas mixture to be analyzed is excited by an electrical pulse signal (excitation signal). During the process, the ions of the gas mixture to be analyzed are brought into the roller coaster movement, where each mass-to-charge ratio (m/z) has a different roller coaster frequency. As in the case of primary ions, these roller coaster movements produce image currents on the cover or measurement electrodes. A Fourier transform can be applied to the measurement signal assigned to the ion, wherein each Fourier frequency can be assigned to a mass-to-charge ratio m/z and assigned to each at a corresponding mass-to-charge ratio m/z signal frequencies level (H f) Department of ions or ion population to be proportional to the respective components of the analysis of the number of ionized particles.
為了最小化離子化期間時間波動對主離子或介穩態粒子的影響，可以採用以下的程序：每個頻率f或每個質荷比m/z之粒子數或訊號位準Hf係藉由以下方程式測定或校正：Hf(校正)=K * Hf(未校正)*H1/ΣHf， (1) In order to minimize the influence of time fluctuations during ionization on the main ion or metastable particles, the following procedure can be used: each frequency f or the number of particles per mass to charge ratio m/z or the signal level H f is The following equation is determined or corrected: H f (corrected) = K * H f (uncorrected) * H1/ΣH f, (1)
其中K表示與質量和頻率無關的校正因子，H1表示在離子阱中被穩定保存和激發的所有離子之訊號位準，Hf(未校正)表示感興趣的 離子或待分析的離子化組分之頻譜位準或訊號位準，以及Σ Hf表示存在於量測光譜中的光譜線之所有訊號位準的總和。校正因子K考量了離子化氣體及/或殘餘氣體及離子化氣體之介穩態粒子的離子數、被以上述方式測定、以及通常為每個氣體脈衝重新計算，以消除或減少可用於離子化將在複數個氣體脈衝之量測上進行分析的氣體混合物的離子或介穩態粒子之波動的影響。在此，量測頻譜之頻譜線可以被限制於位在離子化氣體或殘餘氣體之離子的頻譜之外的質荷比m/z，但此並非強制的。 Wherein K represents the frequency and independent of the mass correction factor, H1 represents the signal being stable for all ions and excited in the ion trap level, H f (uncorrected) represents an ion of interest to be analyzed or ionized components The spectral level or signal level, and Σ H f represents the sum of all signal levels of the spectral lines present in the measurement spectrum. The correction factor K takes into account the ion number of the ionized gas and/or the residual gas and the metastable particles of the ionized gas, is determined in the manner described above, and is typically recalculated for each gas pulse to eliminate or reduce ionization. The effect of fluctuations in the ions or metastable particles of the gas mixture to be analyzed on the measurement of a plurality of gas pulses. Here, the spectral line of the measurement spectrum can be limited to the mass-to-charge ratio m/z outside the spectrum of the ions of the ionized gas or the residual gas, but this is not mandatory.
該質譜儀較佳被體現或程式化來產生氣體混合物之激發離子，而不需激發離子化氣體及/或殘餘氣體之離子，以測定待分析氣體混合物之離子化組分的粒子數。為此目的，選擇該離子阱之激發訊號(電脈衝訊號)，其選擇方式使得在離子化待分析的氣體混合物之後，除了主離子之外所有的離子皆被激發。舉例來說，可以構設此激發訊號，其方式使得離子阱中的主離子變成不穩定並因此離開離子阱，使得只有待分析氣體混合物之離子仍然被激發並保持在阱中。 The mass spectrometer is preferably embodied or programmed to generate excited ions of the gas mixture without exciting ions of the ionized gas and/or residual gas to determine the number of particles of the ionized component of the gas mixture to be analyzed. For this purpose, the excitation signal (electrical pulse signal) of the ion trap is selected in such a way that after ionizing the gas mixture to be analyzed, all ions except the main ion are excited. For example, the excitation signal can be configured in such a way that the main ions in the ion trap become unstable and thus leave the ion trap such that only ions of the gas mixture to be analyzed are still excited and remain in the well.
在進一步的具體實施例中，該質譜儀被體現為測定該離子阱中的待分析離子化氣體混合物之組分的離子數具有小於5%的不精確度。以上進一步描述的、包括測定主離子數的量測程序理論上可以被重複任何次數。由於在每個量測程序中預先對主離子數H1進行正規化並且由於依據方程式(1)用於測定校正的量測訊號的轉換被用在每個量測程序中，故理論上可以完全消除由於離子化的變化或漂移所造成的時間波動。 In a further embodiment, the mass spectrometer is embodied to determine an inaccuracy of less than 5% of the number of ions of the component of the ionized gas mixture to be analyzed in the ion trap. The measurement procedure described further above, including determining the number of primary ions, can theoretically be repeated any number of times. Since the main ion number H1 is previously normalized in each measurement procedure and since the conversion for measuring the corrected measurement signal according to equation (1) is used in each measurement procedure, it can theoretically be completely eliminated. Time fluctuations due to changes or drift in ionization.
在本發明的進一步態樣中，特別是還可以結合上述態樣來實現的進一步態樣中，該離子化氣體為介穩態的鈍氣，尤其是氦。為了加速 量測，前案中嘗試在離子阱中心盡可能快地藉由氣體制動來收集離子。舉例來說，US 2010/0084549 A1描述可以在操作過程中將緩衝氣體引入離子阱，以冷卻離子並將這些離子集中在離子阱的中心。然而，這導致原位量測中的質量解析度大幅衰退(即在離子阱中量測的情況下)，此為先前技藝中的離子檢測通常是在離子阱外部進行的原因。 In a further aspect of the invention, in particular in a further aspect which can also be achieved in connection with the above-described aspect, the ionized gas is a metastable, blunt gas, in particular helium. In order to accelerate Measurements, in the previous case, attempted to collect ions by gas braking as quickly as possible in the center of the ion trap. For example, US 2010/0084549 A1 describes that buffer gas can be introduced into the ion trap during operation to cool the ions and concentrate these ions in the center of the ion trap. However, this results in a significant degradation of the mass resolution in the in-situ measurement (i.e., in the case of measurements in the ion trap), which is why ion detection in the prior art is typically performed outside of the ion trap.
為了實現不變的高質量解析度而不需在該程序中由於離子阱中故意低的工作壓力而等待過長的時間，本發明的態樣提出質譜儀被體現用於以介穩態鈍氣的形式供應離子化氣體之介穩態粒子至離子阱。介穩態鈍氣粒子是處於激發電子態的中性粒子(剛好在實際離子化之前)。結果，介穩態粒子獲得了特別大的橫截面，從而在離子阱中產生較大的、與待分析氣體混合物之組分碰撞的機率。結果，待分析的離子被更迅速地收集在離子阱的中央，而不需要為此目的所需的緩衝氣體產生的較高壓力，所以可以比已知的解決方案明顯更快速地進行量測。發現到氦氣作為介穩態鈍氣是特別有利的。然而，除了諸如He、Ar、Kr及Xe等鈍氣之外，還可以使用例如氫氣(H2)、氮氣(N2)或其混合物作為離子化氣體。這些氣體也可以被引入離子阱中作為介穩態粒子，以將待分析的氣體混合物收集在離子阱的中心。 In order to achieve constant high quality resolution without the need to wait too long in the program due to deliberately low operating pressure in the ion trap, the aspect of the invention proposes that the mass spectrometer is embodied for metastable gas The form supplies the metastable particles of the ionized gas to the ion trap. Metastable blunt particles are neutral particles in an excited electronic state (just before actual ionization). As a result, the metastable particles acquire a particularly large cross section, resulting in a greater probability of collision with the components of the gas mixture to be analyzed in the ion trap. As a result, the ions to be analyzed are collected more rapidly in the center of the ion trap without the need for higher pressures generated by the buffer gas required for this purpose, so that measurements can be made significantly faster than known solutions. It has been found to be particularly advantageous to use helium as a metastable gas. However, in addition to an blunt gas such as He, Ar, Kr, and Xe, for example, hydrogen (H 2 ), nitrogen (N 2 ), or a mixture thereof may be used as the ionized gas. These gases can also be introduced into the ion trap as metastable particles to collect the gas mixture to be analyzed at the center of the ion trap.
在一個發展中，該質譜儀被體現來在每種情況下以至少500amu或1000amu的質量帶寬記錄至少10個頻譜/秒。如以上進一步說明的，使用介穩態粒子可以增加離子化氣體的橫截面或離子化氣體與待分析氣體混合物或與待分析氣體組分的碰撞機率，因而將量測速度提高至上述值。 In one development, the mass spectrometer is embodied to record at least 10 spectra/second in each case with a mass bandwidth of at least 500 amu or 1000 amu. As further explained above, the use of metastable particles can increase the cross-section of the ionized gas or the probability of collision of the ionized gas with the gas mixture to be analyzed or with the gas component to be analyzed, thereby increasing the measurement speed to the above values.
在進一步的具體實施例中，該離子化裝置具有用於產生該離 子化氣體之離子及/或介穩態粒子的電漿源，以供應這些到該離子阱中。舉例來說，該離子化氣體可以被電漿源離子化，該電漿源將該離子化氣體之氣體組分轉化成介穩態電子狀態或離子化。舉例來說，在處理中，鈍氣(例如氦原子)可以被轉化成介穩態狀態或被離子化。該離子化氣體之氣體分子被轉化成離子的部分與被轉化成介穩態粒子的部分之比率可以被具有適當設計的電漿源或適當的製程控制影響，例如被電漿源和離子化氣體之氣流影響。 In a further embodiment, the ionization device has a means for generating the separation A plasma source of ions and/or metastable particles of the gas is supplied to supply the ions into the ion trap. For example, the ionized gas can be ionized by a plasma source that converts the gas component of the ionized gas to a metastable electronic state or ionization. For example, in processing, an blunt gas (eg, a helium atom) can be converted to a metastable state or ionized. The ratio of the portion of the ionized gas that is converted to ions to the portion that is converted to the metastable particles can be affected by a suitably designed plasma source or appropriate process control, such as by a plasma source and an ionized gas. Airflow impact.
發現若電漿及因此離子化氣體之離子或介穩態粒子在離子阱外部的電漿源中產生將是有利的，即若電漿源中的電漿產生及離子阱中待分析氣體混合物之離子化(藉由碰撞離子化或電荷交換離子化)是以空間分離的方式進行，因為此可明顯減少由離子阱中的電漿導致的溫度上升。 It has been found to be advantageous if the plasma or thus the ionized or metastable particles of the ionized gas are produced in a plasma source external to the ion trap, ie if the plasma in the plasma source is generated and the gas mixture to be analyzed in the ion trap Ionization (by collisional ionization or charge exchange ionization) is performed in a spatially separated manner as this significantly reduces the temperature rise caused by the plasma in the ion trap.
該電漿源可被體現為射頻電漿源、中頻電漿源、DC電漿源、介電質阻障放電電漿源、大氣壓電漿源、電暈放電電漿源等。 The plasma source can be embodied as a radio frequency plasma source, an intermediate frequency plasma source, a DC plasma source, a dielectric barrier discharge plasma source, an atmospheric piezoelectric slurry source, a corona discharge plasma source, and the like.
在有利的發展中，電漿源被體現來在低於100℃的溫度下產生離子化氣體的離子及/或介穩態粒子，亦即電漿源中的電漿放電在低溫下(在100℃下)發生。舉例來說，這可以藉由施加交變射頻場(頻率在1MHz和30MHz之間)來實現，因為相應的RF放電可以在10℃和200℃之間的溫度下有利地發生。可以理解的是，也可以使用能夠將(中性)離子化氣體轉化或離子化成激發電子態的不同類型離子化裝置來取代電漿源，以在離子阱中引發氣體混合物的碰撞或電荷交換離子化。特別是可以藉由分析物和介穩態鈍氣粒子之間的電荷交換來實現特別稀少的(冷的)且具有小碎片分析物的離子化。 In an advantageous development, the plasma source is embodied to generate ions and/or metastable particles of the ionized gas at temperatures below 100 ° C, ie plasma discharge in the plasma source at low temperatures (at 100 Occurs at °C). This can be achieved, for example, by applying an alternating RF field (frequency between 1 MHz and 30 MHz), since the corresponding RF discharge can advantageously occur at temperatures between 10 °C and 200 °C. It will be appreciated that different types of ionization devices capable of converting or ionizing (neutral) ionized gases into an excited electronic state may be used in place of the plasma source to induce collision or charge exchange ions of the gas mixture in the ion trap. Chemical. In particular, ionization of particularly rare (cold) and small fragment analytes can be achieved by charge exchange between the analyte and the metastable blunt particles.
由於小碎片分析物的結果，在離子阱中還可以有質量數高達2000000amu的大粒子之粒子量測和特徵化。為此目的，可以利用待檢測質荷比m/z如以下所述取決於離子阱中的保存幅值Vrf(軌跡的直徑)和場頻frf的事實：m/z~Vrf/(frf)2。 As a result of small fragment analytes, particle size and characterization of large particles up to 2,000,000 amu can also be found in the ion trap. For this purpose, the fact that the mass-to-charge ratio m/z to be detected depends on the preservation amplitude V rf (diameter of the trajectory) and the field frequency f rf in the ion trap can be utilized as follows: m/z~V rf /( f rf ) 2 .
因此，可以藉由在離子阱中增加保存幅值Vrf及/或藉由減小場頻frf來量測質量非常大的粒子。 Therefore, very large mass particles can be measured by increasing the preservation amplitude Vrf in the ion trap and/or by reducing the field frequency frf .
在進一步的具體實施例中，該離子化裝置具有用於產生電子的電子束源。特別的是，該電子束源可以被體現來產生具有可變電子能量的電子，該可變電子能量例如在1eV和100eV之間的範圍中。該電子束源(例如處於電子槍形式)還可以配備有聚焦裝置或束導引，以將電子對齊到待分析氣體混合物之氣流上。該電子束源可以被用來取代用於離子化氣體混合物的電漿源，或除了該電漿源之外還可以使用該電子束源。 In a further embodiment, the ionization device has an electron beam source for generating electrons. In particular, the electron beam source can be embodied to produce electrons having variable electron energies, for example in the range between 1 eV and 100 eV. The electron beam source (for example in the form of an electron gun) can also be equipped with a focusing device or beam guide to align the electrons onto the gas stream of the gas mixture to be analyzed. The electron beam source can be used in place of or in addition to the plasma source for the ionized gas mixture.
本發明的進一步態樣(特別是還可以與前述態樣中之一者結合的態樣)係以開端所提出類型的質譜儀實現，其被體現來選擇性移除或抑制離子阱中的具有一質荷比的離子，該離子阱中的離子數超過預定臨界值。為了增加質譜儀的動態範圍，提出了抑制或移除該離子阱中的大離子群體，使得可以更精確地量測離子群體之特定子集。 A further aspect of the invention (particularly also in combination with one of the foregoing aspects) is achieved with a mass spectrometer of the type proposed at the outset, which is embodied to selectively remove or inhibit the presence in the ion trap A mass-to-charge ratio of ions in the ion trap that exceeds a predetermined threshold. In order to increase the dynamic range of the mass spectrometer, it is proposed to suppress or remove large ion populations in the ion trap so that a particular subset of the ion population can be more accurately measured.
舉例來說，在「傅立葉轉換離子迴旋共振」(Fourier Transform Ion Cyclotron Resonance，FT-ICR)阱中，可以藉由所謂的SWIFT(保存波形逆傅立葉轉換(Stored Waveform Inverse Fourier Transform))激發來移除或抑制離子群體，該SWIFT激發例如Tan-Chin Lin Wang等人在Anal.Chem. 1986,58,2935-2938中的文章「傅立葉轉換離子迴旋共振質譜儀中的動態範圍經由保存波形逆傅立葉轉換激發之延伸(Extension of Dynamic Range in Fourier Transform Ion Cyclotron Resonance Mass Spectrometry via Stored Waveform Inverse Fourier Transform Excitation)」所述。此處可以進行同步量測，尤其是在複數個具有不同質荷比的量測區域中。 For example, in the Fourier Transform Ion Cyclotron Resonance (FT-ICR) trap, it can be removed by so-called SWIFT (Stored Waveform Inverse Fourier Transform) excitation. Or suppressing the ion population, the SWIFT excitation is for example Tan-Chin Lin Wang et al. at Anal.Chem. 1986, 58, 2935-2938 "Extension of Dynamic Range in Fourier Transform Ion Cyclotron Resonance Mass Spectrometry via Stored Waveform Inverse Fourier Transform" (Extension of Dynamic Range in Fourier Transform Ion Cyclotron Resonance Mass Spectrometry Excitation)". Synchronous measurements can be made here, especially in a plurality of measurement areas with different mass-to-charge ratios.
該動態範圍還可以在本發明的進一步態樣中增加，尤其是該進一步態樣可以與上述態樣中之一者或更多者結合，而且在該進一步態樣中，開端所提出類型的質譜儀被體現來在質荷比之預定量測範圍中選擇性檢測待分析氣體混合物之離子或離子化組分。這使質量選擇性時間多工量測得以實現，從而同樣使得動態範圍增加成為可能。 The dynamic range may also be increased in a further aspect of the invention, in particular the further aspect may be combined with one or more of the above aspects, and in this further aspect, the mass spectrometer of the type proposed at the beginning The apparatus is embodied to selectively detect ion or ionized components of the gas mixture to be analyzed in a predetermined measurement range of mass to charge ratio. This enables mass-selective time multiplex measurement to also make it possible to increase the dynamic range.
還可以使用進一步更複雜的量測模式(例如兩個上述程序之任意組合(SWIFT或時間多工))，以提高動態。此處，總是必須小心的是量測裝置不超過負荷。 Further more complex measurement modes (eg, any combination of two of the above procedures (SWIFT or time multiplex)) can also be used to increase dynamics. Here, it must always be taken care that the measuring device does not exceed the load.
在一個發展中，該質譜儀具有108(或108：1)或更大的動態範圍。這樣的動態範圍可以藉由使用一個量測方法或兩個上述量測方法的組合來實現。 In one development, the mass spectrometer has a dynamic range of 10 8 (or 10 8 : 1) or greater. Such dynamic range can be achieved by using a measurement method or a combination of two of the above measurement methods.
在一個發展中，該離子阱被體現來累積該氣體混合物之各個離子，並且該質譜儀具有10-15毫巴或更低的(即<10-15毫巴)檢測限制。離子阱質譜儀通常不連續地操作，即離子數的分析可以在預定的累積時間(例如少於100ms)之後發生。特別是，可以視情況地使用離子阱來進行待檢測氣體組分的累積及待檢測氣體組分與其他氣態組分的分離。 In one development, the ion trap is embodied to accumulate individual ions of the gas mixture, and the mass spectrometer has a detection limit of 10 -15 mbar or less (ie, <10 -15 mbar). Ion trap mass spectrometers typically operate discontinuously, i.e., analysis of the number of ions can occur after a predetermined accumulation time (e.g., less than 100 ms). In particular, an ion trap can be used as appropriate to carry out the accumulation of the gas component to be detected and the separation of the gas component to be detected from other gaseous components.
藉由組合上述用於增加動態響應的程序(SWIFT或時間多 工量測)與離子阱的累積能力，可以檢測特別小的/弱的離子群體。在程序中，可以累積個別的離子直到足夠大的量測訊號出現。在已知量測訊號和已知累積時間的情況下，待分析離子群體可以被定量測定。以此方式，質譜儀的檢測極限可以被降到10-15毫巴或更低。 By combining the above-described procedures for increasing the dynamic response (SWIFT or time multiplex measurement) with the accumulation capacity of the ion trap, a particularly small/weak ion population can be detected. In the program, individual ions can be accumulated until a sufficiently large measurement signal appears. The ion population to be analyzed can be quantitatively determined with known measurement signals and known accumulation times. In this way, the detection limit of the mass spectrometer can be reduced to 10 -15 mbar or lower.
本發明之進一步態樣，特別是可以與一個前述態樣結合的進一步態樣係藉由具有壓力降低單元的質譜儀來實現，該壓力降低單元具有至少一個、較佳至少兩個、特別是三個或更多的模組化壓力階段，該等模組化壓力階段可以被串聯連接，用於降低待分析氣體混合物之氣體壓力。依據此態樣，提出了使用一個、兩個或三個(或視情況更多的)壓力階段之模組化設計來實現壓力降低單元，該等壓力階段可以被連接在量測腔室(通常具有離子阱，視情況地還具有傳統的質譜儀，例如四極質譜儀)與具有待分析氣體混合物的腔室之間。取決於應用，這使得能夠串聯連接一個、兩個或三個壓力階段，以降低氣體壓力，使得氣體混合物可以被供應到量測腔室。在具有待分析氣體混合物的腔室中的氣體壓力足夠低(例如<10-5毫巴)的情況下，視情況地可以省略壓力降低單元，即在具有待分析氣體混合物的腔室和量測腔室之間不需要或引入壓力階段。 A further aspect of the invention, in particular a further aspect which can be combined with a preceding aspect, is achieved by a mass spectrometer having a pressure reduction unit having at least one, preferably at least two, in particular three One or more modular pressure stages, which may be connected in series to reduce the gas pressure of the gas mixture to be analyzed. In accordance with this aspect, it is proposed to implement a pressure reduction unit using one, two or three (or more optionally) pressure stages, which can be connected to the measurement chamber (usually There is an ion trap, optionally with a conventional mass spectrometer, such as a quadrupole mass spectrometer, and a chamber having a gas mixture to be analyzed. Depending on the application, this enables one, two or three pressure phases to be connected in series to reduce the gas pressure so that the gas mixture can be supplied to the measurement chamber. In the case where the gas pressure in the chamber with the gas mixture to be analyzed is sufficiently low (for example <10 -5 mbar), the pressure reduction unit can optionally be omitted, ie in the chamber with the gas mixture to be analyzed and the measurement No pressure phase is required or introduced between the chambers.
舉例來說，壓力降低單元可以由三個(或更多的)彼此協調的壓力階段組成，其中該協調可以藉由在每個壓力階段中約100-1000毫巴的壓力降低來實現。在待分析氣體混合物具有高氣體壓力(100巴-10-2毫巴)的情況下可以使用全部三個壓力階段，在該氣體混合物具有中度壓力(10-2毫巴-10-5毫巴)的情況下可以使用兩個該壓力階段，以及在低氣體壓力(<10-5毫巴)的情況下可以只使用一個壓力階段。視情況地，在具 有待分析氣體混合物的腔室中壓力為10-5毫巴或更低的情況下可以省略壓力階段的設置。該等壓力階段具有模組化設計而且可以藉由彼此互連而被串聯連接，例如藉由這些壓力階段以氣密的方式在凸緣上彼此旋緊。以此方式，可以非常快速地拆卸或重組壓力階段，以提供待檢測氣體混合物所需的壓力範圍。 For example, the pressure reduction unit may consist of three (or more) pressure stages that are coordinated with each other, wherein the coordination may be achieved by a pressure drop of about 100-1000 mbar in each pressure stage. All three pressure stages can be used in the case of a gas mixture to be analyzed having a high gas pressure (100 bar - 10 -2 mbar), with a moderate pressure in the gas mixture (10 -2 mbar - 10 -5 mbar) In this case, two pressure phases can be used, and in the case of low gas pressures (<10 -5 mbar), only one pressure phase can be used. Optionally, the setting of the pressure phase can be omitted if the pressure in the chamber having the gas mixture to be analyzed is 10 -5 mbar or less. The pressure stages have a modular design and can be connected in series by interconnecting one another, for example by means of these pressure stages, in a gastight manner on the flanges. In this way, the pressure phase can be disassembled or recombined very quickly to provide the pressure range required for the gas mixture to be tested.
藉由使用一個或更多的壓力階段或藉由不使用壓力階段，能夠使用質譜儀來分析氣體壓力在10-5毫巴和10-15毫巴之間的氣體混合物，而且特別是可以以特別簡單的方式適用於所需的壓力範圍。 By using one or more pressure stages or by not using a pressure stage, it is possible to use a mass spectrometer to analyze a gas mixture having a gas pressure between 10 -5 mbar and 10 -15 mbar, and in particular The simple way to apply to the required pressure range.
本發明之進一步態樣，特別是可以與一個前述態樣結合的進一步態樣係在質譜儀中實現，該質譜儀被體現來在離子阱中重複激發待分析氣體混合物之離子化組分，並在每個激發的情況下在預定的持續時間期間記錄待分析離子化組分之質譜。依據此態樣，提出了利用離子阱質譜儀的選擇來進行多次重複的離子激發，而不需要為此目地使用其他的元件。可以在每個激發期間檢測待分析的離子化組分或記錄質譜。 A further aspect of the invention, and in particular a further aspect that can be combined with a preceding aspect, is achieved in a mass spectrometer that is embodied to repeatedly excite an ionized component of a gas mixture to be analyzed in an ion trap, and The mass spectrum of the ionized component to be analyzed is recorded during a predetermined duration for each excitation. In accordance with this aspect, it has been proposed to use ion trap mass spectrometry to perform multiple repeated ion excitations without the need to use other components for this purpose. The ionized component to be analyzed or the mass spectrum can be recorded during each excitation.
在一個發展中，用於記錄質譜的持續時間為5ms或更短。由於待分析氣體混合物之組分只必須被激發而不是被重新離子化，故可以藉由相應的量測窗口非常快速地記錄質譜，以測得被置換或與離子化組分之激發同步的質譜。這使得可以在化學反應過程中、在這些彼此反應之前量測分析物分子，或可以檢測中間產物，使得可以藉由平移量測窗口來檢測反應動態響應，而且化學反應過程可以被實時成像。 In one development, the duration used to record the mass spectrum is 5 ms or less. Since the components of the gas mixture to be analyzed must only be excited rather than re-ionized, the mass spectrum can be recorded very quickly by the corresponding measurement window to measure the mass spectrum that is replaced or synchronized with the excitation of the ionized component. . This makes it possible to measure the analyte molecules during the chemical reaction, before these react with each other, or to detect the intermediate product so that the reaction dynamic response can be detected by the translational measurement window, and the chemical reaction process can be imaged in real time.
在進一步的具體實施例中，該離子阱係選自於包含以下之群組：傅立葉轉換離子阱，尤其是傅立葉轉換離子迴旋共振阱、潘寧阱(Penning trap)、環形阱(toroidal trap)、保羅阱(Paul trap)、線性阱、軌域阱(orbitrap)、EBIT及RF聚束器。該離子阱較佳係被體現用來檢測該離子阱中保存或累積的離子，特別是藉由使用傅立葉轉換。 In a further embodiment, the ion trap is selected from the group consisting of Fourier-converted ion traps, in particular Fourier-converted ion cyclotron resonance traps, Penning wells (Penning) Trap), toroidal trap, Paul trap, linear trap, orbitrap, EBIT, and RF buncher. The ion trap is preferably embodied to detect ions that are stored or accumulated in the ion trap, particularly by using Fourier transform.
這種離子阱(例如FT離子阱)的使用使得能夠實施快速量測(掃描時間在秒的範圍中或更快，例如在毫秒的範圍中)。在這種類型的阱中，由量測電極上的陷入離子產生的感應電流係以時間相關的方式進行檢測和放大。隨後，此時間相關性被頻率轉換(例如快速傅立葉轉換)轉換進入頻率空間，並且使用離子之共振頻率的質量相關性來將頻譜轉換成質譜。可以進行藉助傅立葉轉換的質譜儀來進行快速量測，原則上使用不同類型的離子阱(例如使用上述的類型)，其中使用所謂離子迴旋共振阱的組合是最常見的。FT-ICR阱構成潘寧阱的發展，其中離子被包圍在交流電場和靜態磁場中。在FT-ICR阱(磁或電ICR阱)中，質譜儀可以藉由迴旋共振激發來操作。在其發展中，潘寧阱也可以使用不同的緩衝氣體進行操作，其中由空間離子分隔進行的質量選擇可以藉由緩衝氣體與利用電雙極場的磁控管激發和利用電四極場的迴旋激發之組合來產生，使得潘寧阱也可以被用於將待檢測物質與其他物質分離。由於在這種類型的阱中的緩衝氣體通常具有運動阻尼，並因此對包圍的離子具有「冷卻」效應，故這種類型的阱也可被稱為「冷卻阱」。 The use of such an ion trap (e.g., FT ion trap) enables rapid measurement (scan time in the range of seconds or faster, such as in the range of milliseconds). In this type of well, the induced current generated by the trapped ions on the measuring electrode is detected and amplified in a time-dependent manner. This time correlation is then converted into frequency space by frequency conversion (eg, fast Fourier transform) and the mass dependence of the resonant frequency of the ions is used to convert the spectrum into a mass spectrum. Rapid measurement can be carried out by means of a Fourier-converted mass spectrometer, in principle using different types of ion traps (for example using the type described above), wherein a combination using so-called ion cyclotron resonance traps is the most common. The FT-ICR well constitutes the development of the Penning Well, in which ions are enclosed in an alternating electric field and a static magnetic field. In an FT-ICR trap (magnetic or electrical ICR trap), the mass spectrometer can be operated by cyclotron resonance excitation. In its development, Penning wells can also be operated with different buffer gases, where mass separation by spatial ion separation can be excited by buffer gas and magnetrons using electric bipolar fields and by maneuvers of electric quadrupole fields A combination of excitations is generated such that the Penning well can also be used to separate the substance to be detected from other substances. This type of well can also be referred to as a "cooling trap" since the buffer gas in this type of trap typically has motion damping and therefore a "cooling" effect on the surrounding ions.
所謂的環形阱可以實現比傳統的四極阱更緊湊的設計，同時基本上具有相同的離子保存容量。線性阱是四極阱或保羅阱發展出的，其中離子不是被保持在三維的四極場中，而是由另外的邊緣場保持在二維的四極場中，以增加離子阱的保存容量。所謂的軌道阱具有一個中心的紡錘 狀電極，由於電吸引的結果離子圍繞該紡錘狀電極並被保持在軌域上，其中沿著中心電極軸的振盪係由偏離中心的離子注射所產生，該振盪在檢測器板中產生訊號，該訊號可以像在FT-ICR阱的情況一樣被檢測(藉由FT)。電子束離子阱(electron beam ion trap，EBIT)是一種離子阱，其中利用離子槍藉由碰撞離子化來產生離子，其中這樣產生的離子被電磁場吸引並被後者捕獲。這些離子也可以被保存在RF(射頻)聚束器，例如所謂的RFQ(四極)聚束器。可以理解的是，除了上面所列類型的阱之外，也可以使用其它類型的離子阱來進行氣體分析，該等其它類型的阱可以被視情況地與使用傅立葉轉換的評估結合。 So-called ring traps can achieve a more compact design than conventional quadrupole wells while having substantially the same ion storage capacity. Linear traps are developed by quadrupole traps or Paul traps in which ions are not held in a three-dimensional quadrupole field, but are held in a two-dimensional quadrupole field by additional fringe fields to increase the ion trap's storage capacity. The so-called orbital trap has a central spindle The electrode, as a result of the electrical attraction, surrounds the spindle electrode and is held on the rail, wherein the oscillation along the center electrode axis is generated by off-center ion injection, which generates a signal in the detector plate, This signal can be detected (by FT) as in the case of the FT-ICR trap. An electron beam ion trap (EBIT) is an ion trap in which ions are generated by collision ionization using an ion gun, wherein the ions thus generated are attracted by an electromagnetic field and captured by the latter. These ions can also be stored in RF (radio frequency) bunchers, such as the so-called RFQ (quadrupole) buncher. It will be appreciated that other types of ion traps may be used for gas analysis in addition to the wells of the type listed above, which may be optionally combined with the evaluation using Fourier transforms.
上述以離子阱為基礎(特別是使用電漿離子化)的質譜儀可以被用於在不同領域中檢測最小量的微量元素：舉例來說，該質譜儀可被用於EUV微影中的氣體混合物之質譜分析。在此用途中，特別是可以分析EUV微影系統(例如在EUV微影設備中)中所含的殘餘氣體，例如檢視其中所含的污染物質。質譜儀在EUV微影中的用途可藉由上面另外列出的以下特徵來致能或促進：●使用連續的、高精準的線上原位校正(不準確度小於5%)之定量量測，用於測定在特定尖峰(質荷比)有多少離子存在於離子阱中，●高動態範圍：高達108或更大(最強和最弱訊號之間的比率)，●低檢測極限：下至10-15毫巴，●待分析的中度壓力範圍：10-15毫巴-103毫巴，具有不變的檢測極限， ●電子碰撞離子化、利用電漿離子化的冷離子化或利用具有少碎片的介穩態粒子的離子化、在低溫(<100℃)下的單一離子化。 The above mass spectrometer based on ion traps (especially using plasma ionization) can be used to detect minimal amounts of trace elements in different fields: for example, the mass spectrometer can be used for gases in EUV lithography Mass spectrometry analysis of the mixture. In this application, in particular, it is possible to analyze residual gases contained in an EUV lithography system (for example in an EUV lithography apparatus), for example to examine the contaminants contained therein. The use of mass spectrometers in EUV lithography can be enabled or facilitated by the following features listed separately: • Quantitative measurement using continuous, highly accurate on-line calibration (inaccuracy of less than 5%), Used to determine how many ions are present in the ion trap at a particular peak (mass-to-charge ratio), ● high dynamic range: up to 10 8 or greater (ratio between the strongest and weakest signals), ● low detection limit: down to 10 -15 mbar, ● Moderate pressure range to be analyzed: 10 -15 mbar - 10 3 mbar, with constant detection limits, ● Electron collision ionization, cold ionization using plasma ionization or utilization Ionization of metastable particles with less fragmentation, single ionization at low temperatures (<100 °C).
舉例來說，當在EUV微影設備中使用質譜儀時，在EUV微影設備之投影系統中的質譜儀之連接位置可以形成在與該投影系統之至少一反射鏡相距小於50cm的距離處，在該EUV微影設備之照明系統中的連接位置可以形成在與該照明系統之至少一反射鏡相距小於50cm的距離處，或在該EUV微影設備之輻射產生系統中的連接位置可以形成在與收集器(反射鏡)、EUV光源、或用於讓來自該輻射產生系統的EUV輻射通過而進入該照明系統的開口相距小於1m、較佳小於50cm的距離處。 For example, when a mass spectrometer is used in an EUV lithography apparatus, the connection position of the mass spectrometer in the projection system of the EUV lithography apparatus may be formed at a distance of less than 50 cm from at least one mirror of the projection system, The connection position in the illumination system of the EUV lithography apparatus may be formed at a distance of less than 50 cm from at least one mirror of the illumination system, or a connection position in the radiation generation system of the EUV lithography apparatus may be formed at The distance from the collector (mirror), the EUV source, or the opening for entering the illumination system through the EUV radiation from the radiation generating system is less than 1 m, preferably less than 50 cm.
若質譜儀的連接位置(其由真空殼體的壁中的開口界定，通常是投影系統、照明系統或輻射產生系統的真空殼體，待分析物質可以經由該開口進入質譜儀)被形成在EUV微影設備的反射鏡附近將是有利的，以能夠以針對性的方式檢測可能會累積在反射鏡之光學表面上的污染物質。連接位置在輻射產生系統和照明系統之間的開口附近的質譜儀配置是有利的，因為能夠測定從輻射產生系統通過進入照明系統的污染物質之比例大小。連接位置在EUV光源附近的質譜儀配置使得能夠檢測或量測EUV光源產生的污染物質。 If the connection position of the mass spectrometer (which is defined by an opening in the wall of the vacuum housing, typically a vacuum housing of a projection system, illumination system or radiation generating system through which the substance to be analyzed can enter the mass spectrometer) is formed in the EUV It will be advantageous to have a mirror near the mirror of the lithography apparatus to be able to detect contaminants that may accumulate on the optical surface of the mirror in a targeted manner. A mass spectrometer configuration that connects the location near the opening between the radiation generating system and the illumination system is advantageous because the proportion of contaminant from the radiation generating system into the illumination system can be determined. The mass spectrometer configuration of the connection location near the EUV source enables detection or measurement of contaminants produced by the EUV source.
在發展中，藉由真空連接將質譜儀與EUV微影設備的殼體分開，EUV微影設備的殼體容納殘餘氣體氛圍並導引EUV輻射，該真空連接具有小於100mm、較佳小於5mm、尤其是小於1mm或小於500μm而且通常超過50μm的橫截面。對於質譜分析，若不將質譜儀和投影系統、照明系統、輻射產生系統或圍繞這些的真空殼體之殼體間的真空連接之橫 截面選擇得太大會是有利的。特別是，這樣的真空連接允許質譜儀的內部被真空泵或真空產生裝置排空，該真空泵或真空產生裝置只有或主要排空質譜儀的內部。 In development, the mass spectrometer is separated from the housing of the EUV lithography apparatus by a vacuum connection, the housing of the EUV lithography apparatus housing a residual gas atmosphere and directing EUV radiation having a vacuum connection of less than 100 mm, preferably less than 5 mm, In particular, a cross section of less than 1 mm or less than 500 μm and usually more than 50 μm. For mass spectrometry, if the mass spectrometer is not connected to the projection system, the illumination system, the radiation generation system, or the vacuum connection between the housings of the vacuum housings surrounding these It may be advantageous to choose a section that is too large. In particular, such a vacuum connection allows the interior of the mass spectrometer to be evacuated by a vacuum pump or vacuum generating device that only or primarily vents the interior of the mass spectrometer.
在進一步的發展中，在該EUV微影設備之殘餘氣體氛圍的殼體中，以下污染物質或其混合物中之至少一者係在該質譜分析期間進行量測或檢測，該殘餘氣體氛圍尤其含有氫及/或氦及/或空氣：氧、臭氧、水、高達10Mamu的CXHYOZ、高達10Mamu的粒子、高達10Mamu的金屬-CXHYOZ化合物，其中1Mamu=1000000amu。 In a further development, in the housing of the residual gas atmosphere of the EUV lithography apparatus, at least one of the following pollutants or a mixture thereof is measured or detected during the mass spectrometry, the residual gas atmosphere particularly containing Hydrogen and/or helium and/or air: oxygen, ozone, water, C X H Y O Z up to 10 Mamu, particles up to 10 Mamu, metal-C X H Y O Z compounds up to 10 Mamu, of which 1 Mamu = 1000000 amu.
本發明還包含EUV微影設備，該EUV微影設備被體現作為上述的EUV微影設備並結合使用該質譜儀。 The present invention also encompasses an EUV lithography apparatus that is embodied as the EUV lithography apparatus described above in combination with the mass spectrometer.
該質譜儀之進一步用途係關於在塗佈設備之塗佈製程期間進行氣體混合物之質譜分析，該氣體混合物可以含有例如製程氣體。特別是，上述質譜儀可以具有自清洗功能，以去除在量測室或離子阱中形成的沉積物，該沉積物係由待分析氣體混合物、尤其是製程氣體所形成的。由於選擇自清洗的結果，該質譜儀可被用於許多的塗佈製程。其小的安裝空間(約300mm高×約300mm寬及約200-300mm深)構成了本文所述質譜儀之進一步特別的特徵。這使得能夠將該質譜儀使用在安裝空間扮演重要角色的許多應用中(例如MOCVD，參見以下)。 A further use of the mass spectrometer relates to mass spectrometry of a gas mixture during a coating process of a coating apparatus, which gas mixture may contain, for example, a process gas. In particular, the mass spectrometer described above may have a self-cleaning function to remove deposits formed in the measurement chamber or ion trap formed by the gas mixture to be analyzed, particularly the process gas. The mass spectrometer can be used in many coating processes due to the choice of self-cleaning. Its small mounting space (about 300 mm high x about 300 mm wide and about 200-300 mm deep) constitutes a further particular feature of the mass spectrometer described herein. This enables the mass spectrometer to be used in many applications where the installation space plays an important role (eg MOCVD, see below).
舉例來說，自清洗可以如WO 02/00962 A1中所說明的發生，WO 02/00962 A1描述一種用於移除晶圓生產設備中的製程監測單元之樣品室中的製程氣體所產生的沉積物之原位清洗系統。當必要時，在樣品室中的一個或更多個分析期間沉積的沉積物可以藉由清洗氣體移除。在樣 品室產生電漿的過程中，清洗氣體與沉積物形成氣態的清洗產物，該清洗產物被從樣品室移除。 For example, self-cleaning can occur as described in WO 02/00962 A1, which describes a deposition for the removal of process gases in a sample chamber of a process monitoring unit in a wafer production facility. In-situ cleaning system. When necessary, deposits deposited during one or more analyses in the sample chamber may be removed by the purge gas. Sample During the plasma generation of the chamber, the purge gas and the deposit form a gaseous cleaning product that is removed from the sample chamber.
在上述用途的發展中，該塗佈製程係選自於包含以下製程之群組：化學氣相沉積(chemical vapour deposition，CVD)、金屬有機化學氣相沉積(metal organic chemical vapour deposition，MOCVD)、金屬有機化學氣相磊晶(metal organic chemical vapour phase epitaxy，MOVPE)、電漿輔助化學氣相沉積(plasma enhanced chemical vapour deposition，PECVD)、原子層沉積(atomic layer deposition，ALD)、物理氣相沉積(physical vapour deposition，PVD)、(特別是電漿輔助的)蝕刻和植入製程及分子束磊晶(molecular beam epitaxy，MBE)製程。 In the development of the above applications, the coating process is selected from the group consisting of chemical vapor deposition (CVD), metal organic chemical vapour deposition (MOCVD), Metal organic chemical vapour phase epitaxy (MOVPE), plasma enhanced chemical vapour deposition (PECVD), atomic layer deposition (ALD), physical vapor deposition (physical vapour deposition, PVD), (especially plasma-assisted) etching and implantation processes, and molecular beam epitaxy (MBE) processes.
質譜儀在此應用領域的用途可藉由上面另外列出的以下特徵來致能或促進：●高動態範圍：高達108或更大(最大/最小訊號之間的比率)，●高掃描速度：高達10個頻譜/秒或更高，且質量帶寬高達約1000amu，●低檢測極限：下至10-15毫巴，●待分析的中度壓力範圍：10-15毫巴-103毫巴，具有不變的檢測極限，●電子碰撞離子化、利用電漿離子化的冷離子化或利用具有少碎片的介穩態粒子的離子化、在低溫(<100℃)下的單一離子化，●適當的快速量測程序(在毫秒範圍)使得能夠實時拍攝實際的化學製程，●製程室中的粒子量測和特徵化， ●藉由適當的清洗製程進行質譜儀的自清洗。 The use of mass spectrometers in this field of application can be enabled or facilitated by the following features additionally listed above: • High dynamic range: up to 10 8 or greater (ratio between maximum/minimum signals), • High scanning speed : Up to 10 spectra/second or higher with a mass bandwidth of up to approximately 1000 amu, ● Low detection limit: down to 10 -15 mbar, ● Moderate pressure range to be analyzed: 10 -15 mbar - 10 3 mbar , with constant detection limits, ● electron impact ionization, cold ionization with plasma ionization, or ionization with metastable particles with less fragmentation, single ionization at low temperatures (<100 ° C), • Proper rapid measurement procedures (in the millisecond range) enable real-time capture of actual chemical processes, • particle measurement and characterization in the process chamber, • self-cleaning of the mass spectrometer with appropriate cleaning processes.
在一個發展中，在塗佈設備中質譜儀的納入位置被形成在氣體供應系統中、在氣體混合系統中或在氣體處置系統中，特別是在氣體處置系統的真空泵的上游或下游，及/或與製程室相距短於1m、較佳短於50cm處。特別的是，質譜儀可以被直接連接到製程室。此外，該質譜儀(或其他的質譜儀)可以被連接在氣體供應系統中、在氣體混合系統中或在氣體處置系統中，特別是在製程室和真空泵之間的真空管線中，直接在真空泵的上游或在真空泵下游的排氣管線中。藉由適當地選擇納入位置，該製程可以視需要而被影響，也就是說可以在質譜分析結果的基礎上(特別是)控制或調節該製程。 In one development, the incorporation position of the mass spectrometer in the coating apparatus is formed in a gas supply system, in a gas mixing system, or in a gas disposal system, particularly upstream or downstream of a vacuum pump of a gas treatment system, and/ Or it is shorter than 1m, preferably shorter than 50cm from the process chamber. In particular, the mass spectrometer can be directly connected to the process chamber. In addition, the mass spectrometer (or other mass spectrometer) can be connected in a gas supply system, in a gas mixing system or in a gas disposal system, particularly in a vacuum line between the process chamber and the vacuum pump, directly in the vacuum pump Upstream or in the exhaust line downstream of the vacuum pump. By appropriately selecting the incorporation position, the process can be affected as needed, that is, the process can be controlled or adjusted based on the results of the mass spectrometry.
當在塗佈設備中使用該質譜儀時，在質譜分析期間可以量測以下物質、其混合物及/或反應產物、團簇及/或化合物中之至少一者：H2、He、N2、O2、PH3、AsH3、B、P、As、CH4、CO、CO2、Ar、SCl4、SiHCl3、SiH2Cl2、H2O、CxHy、三甲基鎵、三乙基鎵、三甲基鋁、三乙基鋁、三甲基銦、三乙基銦、Cp2Mg、SiH4、Si2H6、四丁基銨、四丁基矽烷、Xe同位素、Kr同位素、六甲基二矽氧烷、叔丁基胂、三甲基胂、二乙基-叔丁基胂、二乙基-叔丁基膦、二-叔丁基膦、叔丁基肼、二甲基肼、銦、鋁、鎵、硼、矽、金、銻、鉍。 When the mass spectrometer is used in a coating apparatus, at least one of the following, a mixture thereof, and/or a reaction product, a cluster, and/or a compound can be measured during mass spectrometry: H 2 , He, N 2 , O 2 , PH 3 , AsH 3 , B, P, As, CH 4 , CO, CO 2 , Ar, SCl 4 , SiHCl 3 , SiH 2 Cl 2 , H 2 O, C x H y , trimethylgallium, Triethylgallium, trimethylaluminum, triethylaluminum, trimethylindium, triethylindium, Cp 2 Mg, SiH 4 , Si 2 H 6 , tetrabutylammonium, tetrabutylnonane, Xe isotope, Kr isotope, hexamethyldioxane, tert-butyl fluorene, trimethyl hydrazine, diethyl-tert-butyl fluorene, diethyl-tert-butylphosphine, di-tert-butylphosphine, tert-butyl fluorene , dimethyl hydrazine, indium, aluminum, gallium, boron, antimony, gold, antimony, antimony.
在一個發展中，該至少一種物質、混合物、反應產物、團簇及/或化合物係在15℃和5000℃之間、較佳在100℃和2000℃之間的製程室溫度並在10-10毫巴和5巴之間、較佳在10-8毫巴和1巴之間的製程室壓力下進行量測。 In one development, the at least one substance, mixture, reaction product, cluster, and/or compound is at a process chamber temperature between 15 ° C and 5000 ° C, preferably between 100 ° C and 2000 ° C and at 10 -10 The measurement is carried out at a process chamber pressure between mbar and 5 bar, preferably between 10 -8 mbar and 1 bar.
本發明還包含塗佈設備，該塗佈設備被體現作為上述的塗佈設備並結合使用該質譜儀。 The present invention also encompasses a coating apparatus that is embodied as the above-described coating apparatus in combination with the mass spectrometer.
上述質譜儀之進一步用途在於樣品之分析、製備、處理、修飾及/或操作的領域。在此情況下，該質譜儀可供例如用於氣體及/或殘餘氣體監測或用於監測、分析及/或調整供用於樣品之分析、製備、處理、修飾及/或操作的裝置。舉例來說，該裝置可以是多光束儀器，其中例如電子束及/或離子束柱、雷射束、x射線束、光子束等可被替代使用，以製備、處理、修飾及/或操作以及視情況地分析樣品。該裝置也可以是用於表面掃描分析的裝置，該用於表面掃描分析的裝置也可以視情況地被整合到多光束儀器。 Further uses of the above mass spectrometers are in the field of analysis, preparation, processing, modification and/or manipulation of samples. In this case, the mass spectrometer can be used, for example, for gas and/or residual gas monitoring or for monitoring, analyzing and/or adjusting the means for analysis, preparation, processing, modification and/or operation of the sample. For example, the device can be a multi-beam instrument in which, for example, an electron beam and/or ion beam column, a laser beam, an x-ray beam, a photon beam, etc. can be used instead, in preparation, processing, modification, and/or operation, and Samples were analyzed as appropriate. The device may also be a device for surface scanning analysis, which may also be integrated into a multi-beam instrument as appropriate.
上述質譜儀之進一步用途在於化學學科中的氣體分析領域，更精確來說是在化學製程分析的領域。 Further uses of the above mass spectrometers are in the field of gas analysis in the chemical sciences, more precisely in the field of chemical process analysis.
質譜儀在此應用領域的用途可藉由上面另外列出的以下特徵來致能或促進：●使用連續的、高精準的線上原位校正(不準確度小於5%)之定量量測，用於測定在特定尖峰(質荷比)有多少離子存在於離子阱中，●高掃描速度：高達10個頻譜/秒或更高，且質量帶寬高達約1000amu，●高動態範圍：高達108或更大(最大/最小訊號之間的比率)，●低檢測極限：下至10-15毫巴，●待分析的中度壓力範圍：10-15毫巴-103毫巴，具有不變的檢測 極限，●電子碰撞離子化、利用電漿離子化的冷離子化或利用具有少碎片的介穩態粒子的離子化、在低溫(<100℃)下的單一離子化，●適當的快速量測程序(在毫秒範圍)使得能夠實時拍攝實際的化學製程。 The use of mass spectrometers in this field of application can be enabled or facilitated by the following features listed separately: • Quantitative measurement using continuous, highly accurate on-line calibration (inaccuracy of less than 5%) To determine how many ions are present in the ion trap at a particular peak (mass-to-charge ratio), high scanning speed: up to 10 spectra/second or higher, and mass bandwidth up to about 1000 amu, ● high dynamic range: up to 10 8 or Larger (ratio between maximum/minimum signal), ● low detection limit: down to 10 -15 mbar, ● medium pressure range to be analyzed: 10 -15 mbar - 10 3 mbar, with constant Detection limits, ● electron impact ionization, cold ionization using plasma ionization, or ionization using metastable particles with less fragmentation, single ionization at low temperatures (<100 ° C), ● appropriate rapid amount The test program (in the millisecond range) enables real-time shooting of the actual chemical process.
上述質譜儀之進一步用途在於通常是機械振動之振動檢測或振動分析的領域。特別是，該質譜儀可被用於檢測或分析範圍在約1Hz和約15kHz之間的振動。特別是，振動可以是設置或裝置的自然振動，將質譜儀安裝於該設置或裝置的內部，即在質譜儀的使用點檢測振動，而且質譜儀被用來作為振動感測器。為此目的，使用質譜儀來記錄待分析的振動頻率所在的頻率範圍內的頻譜。舉例來說，這種頻譜可以在約1Hz和約15kHz之間。複數個寄生頻率通常位在此頻率範圍內，該等寄生頻率是由機械振動產生的，而且可以藉由例如FT離子阱(特別是FT-ICR阱)的量測電極進行檢測和分析。舉例來說，為了分析振動，一旦質譜儀被安裝到裝置中即可記錄頻譜。假使該裝置在安裝的時候是處在良好的工作秩序中，則此頻譜可以作為參考頻譜。可以在稍後的時間或在幾個稍後的時間重複量測頻譜，並將測得的頻譜與參考頻譜進行比較。假使在測得的頻譜中檢測到一個或更多個另外的線或尖峰，則表示在裝置中的某處發生不良的振動，該不良的振動例如可被回溯到機械問題。舉例來說，振動可以是配置在質譜儀附近、例如(真空)泵的滑動軸承或球軸承之不良自然振動，或由電源單元引起的振動(電源的嗡嗡聲)。 A further use of the above mass spectrometer is in the field of vibration detection or vibration analysis, which is usually mechanical vibration. In particular, the mass spectrometer can be used to detect or analyze vibrations ranging between about 1 Hz and about 15 kHz. In particular, the vibration can be the natural vibration of the setup or device, the mass spectrometer being mounted inside the setup or device, i.e., the vibration is detected at the point of use of the mass spectrometer, and the mass spectrometer is used as a vibration sensor. For this purpose, a mass spectrometer is used to record the frequency spectrum in the frequency range in which the vibration frequency to be analyzed lies. For example, such a spectrum can be between about 1 Hz and about 15 kHz. A plurality of spurious frequencies are typically located in this frequency range, which are generated by mechanical vibration and can be detected and analyzed by a measuring electrode such as an FT ion trap (especially an FT-ICR trap). For example, to analyze vibration, the spectrum can be recorded once the mass spectrometer is installed in the device. This spectrum can be used as a reference spectrum if the device is in good working order at the time of installation. The spectrum can be measured at a later time or at a later time, and the measured spectrum is compared to the reference spectrum. If one or more additional lines or spikes are detected in the measured spectrum, it indicates that a bad vibration has occurred somewhere in the device, which can be traced back to mechanical problems, for example. For example, the vibration may be a bad natural vibration disposed near a mass spectrometer, such as a sliding bearing or a ball bearing of a (vacuum) pump, or a vibration caused by a power supply unit (a click of a power source).
理解的是，上述質譜儀的用途並不限於上述的使用領域，而 是該質譜儀也可被有利地使用於其它的使用領域。 It is understood that the use of the above mass spectrometer is not limited to the above-mentioned fields of use, and It is the mass spectrometer that can also be advantageously used in other fields of use.
本發明還關於一種用於氣體混合物之質譜分析的方法，包含以下的方法步驟：供應離子化氣體之離子及/或介穩態粒子及/或電子至離子阱，測定存在於該離子阱中的該離子化氣體之離子及/或介穩態粒子的數量及/或測定存在於該離子阱中的殘餘氣體之離子的數量，供應待分析的該氣體混合物至該離子阱，特別是以脈衝的方式，以及考量該離子化氣體的離子及/或介穩態粒子之測得數量及/或該殘餘氣體的離子之數量來測定待分析氣體混合物之離子化組分的粒子數(或與該粒子數成比例的訊號)。 The invention further relates to a method for mass spectrometry of a gas mixture, comprising the steps of: supplying ions and/or metastable particles and/or electrons to an ion trap of an ionized gas, and determining the presence in the ion trap The number of ions and/or metastable particles of the ionized gas and/or the amount of ions of the residual gas present in the ion trap, the gas mixture to be analyzed being supplied to the ion trap, in particular pulsed And determining the number of particles (or with the particle) of the ionized component of the gas mixture to be analyzed, taking into account the measured quantity of ions and/or metastable particles of the ionized gas and/or the number of ions of the residual gas a proportional signal.)
如以上結合本發明的第一態樣進一步說明的，可以使用連續的高精度原位校正藉由測定存在於離子阱中的主離子數量來定量分析待分析氣體混合物之組分，所以可以測定離子的數量(對應於頻譜中的尖峰)，該離子數量係在特定的質荷比下以高精度檢測到的。通常情況下，此處可實現小於5%的不準確度，即所量測的值與存在離子阱的樣品容積中的氣體組分之實際(離子化)粒子數量相差不超過5%(高於或低於實際數量)。 As further described above in connection with the first aspect of the invention, continuous high precision in situ calibration can be used to quantify the composition of the gas mixture to be analyzed by determining the amount of primary ions present in the ion trap, so ions can be determined The number (corresponding to a spike in the spectrum), the number of ions detected with high accuracy at a specific mass-to-charge ratio. Typically, less than 5% inaccuracy can be achieved here, ie the measured value differs from the actual (ionized) particle number of the gas component in the sample volume in the ion trap by no more than 5% (higher than Or less than the actual amount).
在該方法的過程中，通常進行以下的程序：最初，在離子阱中累積主離子。在該累積之後激發該等主離子，然後量測主離子的數量。另外地或替代地，可以測定離子阱中的介穩態粒子之數量。在離子化氣體大致上以介穩態粒子的形式存在的前提下，介穩態粒子之數量係與離子阱中的整體壓力成比例，因為可以忽略殘餘氣體的壓力。舉例來說，可以藉由縮短離子瞬態的時間(時間常數)來以高精度測定整體壓力。然後可以在壓力的基礎上推算實際存在於離子阱中的離子化氣體之介穩態粒子數 量。 In the course of this method, the following procedure is usually performed: initially, the main ions are accumulated in the ion trap. The main ions are excited after the accumulation, and then the amount of the main ions is measured. Additionally or alternatively, the amount of metastable particles in the ion trap can be determined. Under the premise that the ionized gas is substantially in the form of metastable particles, the amount of metastable particles is proportional to the overall pressure in the ion trap because the pressure of the residual gas can be ignored. For example, the overall pressure can be measured with high precision by shortening the time (time constant) of the ion transient. The number of metastable particles of the ionized gas actually present in the ion trap can then be estimated on the basis of pressure. the amount.
在激發主離子和量測主離子及/或介穩態粒子的數量同時，平行產生待分析氣體混合物的氣體脈衝，並且後者移動到離子阱。此處，所生產的氣體脈衝通常與主離子數量及/或介穩態粒子數量的量測同步，其方式使得氣體脈衝在主離子及/或介穩態粒子的數量量測完成的時候(或正好之後)到達離子阱。 While exciting the primary ions and measuring the amount of primary ions and/or metastable particles, gas pulses of the gas mixture to be analyzed are generated in parallel, and the latter moves to the ion trap. Here, the gas pulses produced are typically synchronized with the measurement of the number of primary ions and/or the number of metastable particles in such a way that the gas pulse is measured at the completion of the amount of primary ions and/or metastable particles (or Just after) arrive at the ion trap.
氣體脈衝輸送的氣體混合物正好在要進入離子阱之前在離子阱中或視情況地在量測室中利用主離子及/或介穩態粒子或電子藉由碰撞離子化及/或電荷交換離子化進行離子化。在隨後的步驟中，氣體混合物的離子被激發。在氣體混合物的離子的激發過程中或之前，可以憑藉所產生的適當激發訊號移除或抑制離子阱中的主離子。在隨後的步驟中，量測或檢測氣體混合物的激發離子。原則上，以上規範的製程可以視需要時常重複進行。由於在檢測過程中離子沒有被轉化成中性粒子，故也可以在氣體混合物離子化之後重複激發離子阱中的氣體混合物之離子，而沒有必要為此目的進行氣體混合物的新離子化。 The gaseous pulse-delivered gas mixture utilizes ionization and/or charge exchange ionization of the primary ion and/or metastable particles or electrons in the ion trap or optionally in the measurement chamber just prior to entering the ion trap. Ionization is carried out. In a subsequent step, the ions of the gas mixture are excited. The primary ions in the ion trap can be removed or suppressed by the appropriate excitation signal generated during or prior to the excitation of the ions of the gas mixture. In a subsequent step, the excited ions of the gas mixture are measured or detected. In principle, the process of the above specifications can be repeated as often as needed. Since the ions are not converted into neutral particles during the detection, it is also possible to repeatedly excite the ions of the gas mixture in the ion trap after ionization of the gas mixture, without the need for new ionization of the gas mixture for this purpose.
在顯示本發明必要細節的圖式中的圖之基礎上，本發明的進一步特徵和優點可從以下本發明的示例性具體實施例之描述及申請專利範圍中顯現。在每種情況下，各個特徵可以自行實現或在本發明的變型中以任意的組合一起實現。 Further features and advantages of the present invention will become apparent from the following description of the exemplary embodiments of the invention. In each case, the individual features may be implemented by themselves or in any combination of the invention in any combination.
1‧‧‧質譜儀 1‧‧‧Mass Spectrometer
2‧‧‧氣體混合物 2‧‧‧ gas mixture
2a‧‧‧氣體脈衝 2a‧‧‧ gas pulse
3a‧‧‧物質 3a‧‧‧ Substance
3b‧‧‧粒子 3b‧‧‧ particles
3a、3b‧‧‧離子化組分 3a, 3b‧‧‧ ionized components
4‧‧‧出口 4‧‧‧Export
5‧‧‧可控閥 5‧‧‧Controllable valve
6‧‧‧入口 6‧‧‧ entrance
7‧‧‧量測室 7‧‧‧Measurement room
8‧‧‧腔室 8‧‧‧ chamber
10‧‧‧離子阱 10‧‧‧Ion trap
11‧‧‧壓力降低單元 11‧‧‧pressure reduction unit
11a‧‧‧模組化壓力階段 11a‧‧‧Modular pressure stage
11b‧‧‧模組化壓力階段 11b‧‧‧Modular pressure stage
11c‧‧‧模組化壓力階段 11c‧‧‧Modular pressure stage
12‧‧‧離子化裝置 12‧‧‧Ionization device
13‧‧‧離子化氣體 13‧‧‧Ionized gas
13a‧‧‧離子 13a‧‧‧ ions
13b‧‧‧介穩態粒子 13b‧‧‧Mesogenic particles
14‧‧‧殘餘氣體 14‧‧‧Residual gas
14a‧‧‧離子 14a‧‧‧ ions
15‧‧‧計量閥 15‧‧‧ metering valve
16‧‧‧氣體供應管線 16‧‧‧ gas supply pipeline
17‧‧‧氣體貯槽 17‧‧‧ gas storage tank
18‧‧‧電漿源 18‧‧‧ Plasma source
19‧‧‧控制裝置 19‧‧‧Control device
20‧‧‧電子束源 20‧‧‧Electronic beam source
20‧‧‧電極 20‧‧‧ electrodes
20a‧‧‧電子 20a‧‧‧Electronics
21‧‧‧電極 21‧‧‧ electrodes
22‧‧‧放大器 22‧‧‧Amplifier
23‧‧‧FFT光譜儀 23‧‧‧FFT Spectrometer
101‧‧‧EUV微影設備 101‧‧‧EUV lithography equipment
102‧‧‧殼體 102‧‧‧ housing
102‧‧‧輻射產生系統 102‧‧‧radiation generating system
102a‧‧‧殘餘氣體氛圍 102a‧‧‧Residual gas atmosphere
103‧‧‧照明系統 103‧‧‧Lighting system
103a‧‧‧殘餘氣體氛圍 103a‧‧‧Residual gas atmosphere
104‧‧‧投影系統 104‧‧‧Projection system
104a‧‧‧殘餘氣體氛圍 104a‧‧‧Residual gas atmosphere
105‧‧‧EUV光源 105‧‧‧EUV light source
106‧‧‧EUV輻射 106‧‧‧EUV radiation
107‧‧‧準直器 107‧‧‧ collimator
107‧‧‧收集器 107‧‧‧ Collector
108‧‧‧單色器 108‧‧‧ Monochromator
109‧‧‧第一反射光學元件 109‧‧‧First reflective optics
109‧‧‧反射鏡 109‧‧‧Mirror
110‧‧‧第二反射光學元件 110‧‧‧Second reflective optical element
110‧‧‧反射鏡 110‧‧‧Mirror
111‧‧‧光學元件 111‧‧‧Optical components
111‧‧‧光罩 111‧‧‧Photomask
112‧‧‧晶圓 112‧‧‧ wafer
113‧‧‧第三反射光學元件 113‧‧‧ Third reflective optics
113‧‧‧反射鏡 113‧‧‧Mirror
114‧‧‧第四反射光學元件 114‧‧‧Fourth reflective optics
114‧‧‧反射鏡 114‧‧‧Mirror
115‧‧‧真空泵 115‧‧‧Vacuum pump
116‧‧‧光學元件 116‧‧‧Optical components
116‧‧‧通道開口 116‧‧‧Channel opening
201‧‧‧裝置 201‧‧‧ device
202‧‧‧基板 202‧‧‧Substrate
203‧‧‧架座 203‧‧‧ pedestal
204‧‧‧內部 204‧‧‧Internal
205‧‧‧製程室 205‧‧‧Processing Room
206‧‧‧容器 206‧‧‧ Container
207‧‧‧可控閥 207‧‧‧Controllable valve
208‧‧‧容器 208‧‧‧ container
209a‧‧‧可控閥 209a‧‧‧Controllable valve
209b‧‧‧可控閥 209b‧‧‧Controllable valve
210‧‧‧分配器歧管 210‧‧‧Distributor manifold
211‧‧‧可控閥 211‧‧‧Controllable valve
212‧‧‧真空泵 212‧‧‧Vacuum pump
213‧‧‧氣體處置系統 213‧‧‧Gas disposal system
214‧‧‧HfO2塗層 214‧‧‧HfO 2 coating
215‧‧‧控制裝置 215‧‧‧Control device
215‧‧‧氣體混合系統 215‧‧‧ gas mixing system
216‧‧‧氣體供應系統 216‧‧‧ gas supply system
216a‧‧‧供應管線 216a‧‧‧Supply pipeline
216b‧‧‧供應管線 216b‧‧‧Supply pipeline
A‧‧‧橫截面 A‧‧‧ cross section
B‧‧‧磁場 B‧‧‧ Magnetic field
D‧‧‧距離 D‧‧‧Distance
EA-EG‧‧‧納入位置 E A -E G ‧‧‧Inclusion location
H1‧‧‧訊號位準 H1‧‧‧ signal level
Hf‧‧‧訊號位準 H f ‧‧‧ signal level
I‧‧‧電流 I‧‧‧current
MB1...MBx‧‧‧預定量測範圍 MB1...MBx‧‧‧Predetermined measurement range
MS1...MSx‧‧‧質譜 MS1...MSx‧‧‧Mass Spectrometry
P0‧‧‧氣體壓力 P 0 ‧‧‧ gas pressure
PB‧‧‧連接位置 P B ‧‧‧ Connection location
PL1‧‧‧第一連接位置 P L1 ‧‧‧first connection position
PL2‧‧‧第二連接位置 P L2 ‧‧‧second connection position
PL3‧‧‧第三連接位置 P L3 ‧‧‧ third connection position
PS‧‧‧連接位置 P S ‧‧‧ Connection location
SA‧‧‧脈衝激發訊號 SA‧‧‧ pulse excitation signal
SW‧‧‧臨界值 SW‧‧‧ threshold
d‧‧‧厚度 D‧‧‧thickness
f‧‧‧頻率 F‧‧‧frequency
t0‧‧‧時間 t 0 ‧‧‧ time
t1-tx‧‧‧時間 T1-tx‧‧‧Time
τ‧‧‧時間常數 Τ‧‧‧ time constant
△Tm1、...△Tmx‧‧‧預定持續時間 △Tm 1 ,...△Tm x ‧‧‧ scheduled duration
λB‧‧‧操作波長 λ B ‧‧‧Operating wavelength
示例性的具體實施例被描繪在示意圖中，而且將在以下的描 述中進行說明。其細節在於：圖1顯示用於氣體混合物之質譜分析的質譜儀之示意圖；圖2顯示圖1中的質譜儀之離子阱的示例性具體實施例之示意圖；圖3顯示離子阱中的量測程序之時間的示意圖；圖4顯示用於評估質譜的量測程序，其中量測窗口被移動以實現快速量測；圖5a、圖5b顯示藉由SWIFT方法或藉由質量選擇時間多工量測評估的2個質譜；圖6顯示具有質譜儀的EUV微影設備之示意圖；以及圖7顯示用於在基板上進行原子層沉積且具有質譜儀的裝置之示意圖。 Exemplary embodiments are depicted in the schematic and will be described below The description will be made in the description. The details are: Figure 1 shows a schematic diagram of a mass spectrometer for mass spectrometry of a gas mixture; Figure 2 shows a schematic diagram of an exemplary embodiment of the ion trap of the mass spectrometer of Figure 1; Figure 3 shows the measurement in an ion trap Schematic diagram of the time of the program; Figure 4 shows a measurement procedure for evaluating the mass spectrum, wherein the measurement window is moved to achieve fast measurement; Figure 5a, Figure 5b shows the time multiplex measurement by SWIFT method or by quality 2 mass spectra evaluated; Figure 6 shows a schematic of an EUV lithography apparatus with a mass spectrometer; and Figure 7 shows a schematic of an apparatus for atomic layer deposition on a substrate with a mass spectrometer.
在以下對圖式的描述中，相同的元件符號用於相同或功能上等同的元件。 In the following description of the drawings, the same element symbols are used for the same or functionally equivalent elements.
圖1示意性圖示質譜儀1，質譜儀1被連接到腔室8，或質譜儀1可以被連接到腔室8，腔室8中放置將被分析的氣體混合物2。舉例來說，腔室8(在圖1中僅繪示一部分的腔室8)可以是形成工業設備的一部分的製程腔室，該工業設備中係進行工業製程。或者，腔室8可以是例如微影設備的(真空)殼體或其中放置待分析氣體混合物2的不同類型腔室。在圖示的實例中，氣體混合物2具有物質3a和粒子3b，物質3a以氣 相存在(即氣體)並具有<100的原子質量數，粒子3b的質量數在100以上。 Figure 1 schematically illustrates a mass spectrometer 1 to which a mass spectrometer 1 is connected, or a mass spectrometer 1 can be connected to a chamber 8 in which a gas mixture 2 to be analyzed is placed. For example, the chamber 8 (only a portion of the chamber 8 is depicted in FIG. 1) may be a process chamber that forms part of an industrial facility in which the industrial process is performed. Alternatively, the chamber 8 may be a (vacuum) housing such as a lithography apparatus or a different type of chamber in which the gas mixture 2 to be analyzed is placed. In the illustrated example, the gas mixture 2 has a substance 3a and a particle 3b, and the substance 3a is gas The phase exists (ie, gas) and has an atomic mass of <100, and the mass of the particle 3b is 100 or more.
腔室具有出口4，出口4可以經由屬於質譜儀1的可控閥5被連接到量測室7的入口6。在圖1圖示的質譜儀1中，氣體混合物2未經先前離子化即被直接引入作為量測單元的離子阱10中。離子化裝置12用以在離子阱10中借助被供應到離子阱10的離子化氣體13之離子13a及/或介穩態或激發的粒子13b來直接離子化氣體混合物2，該等離子及/或粒子藉由電荷交換或碰撞離子化來離子化氣體混合物2，通常是在離子阱10中進行。圖1中圖示的離子化裝置12還具有形式為產生電子20a的電子束槍之電子束源20，電子20a具有範圍在例如1eV和100eV之間的可變電子能量，該電子束源可以外加於電漿源18使用或用作電漿源18的替代件，並以虛線繪示於圖1中。電子20a用以在離子阱10中藉由電子碰撞離子化直接離子化氣體混合物2。在此方式，待分析的氣體混合物2可以在量測單元(離子阱10)中直接被離子化、視情況累積及量測，而不需要將離子化的氣體混合物輸入離子阱10中。或者，也可以在直接鄰近離子阱10處離子化氣體混合物2，其中在後者的情況下需要將離子化的氣體混合物輸送到離子阱10。 The chamber has an outlet 4 which can be connected to the inlet 6 of the measuring chamber 7 via a controllable valve 5 belonging to the mass spectrometer 1. In the mass spectrometer 1 illustrated in Fig. 1, the gas mixture 2 is directly introduced into the ion trap 10 as a measuring unit without prior ionization. The ionization device 12 is used to directly ionize the gas mixture 2 in the ion trap 10 by means of ions 13a and/or metastable or excited particles 13b supplied to the ionization gas 13 of the ion trap 10, the plasma and/or The particles ionize the gas mixture 2 by charge exchange or collision ionization, typically in the ion trap 10. The ionization device 12 illustrated in Figure 1 also has an electron beam source 20 in the form of an electron beam gun that produces electrons 20a having a variable electron energy ranging between, for example, 1 eV and 100 eV, which may be added The plasma source 18 is used or used as an alternative to the plasma source 18 and is shown in dashed lines in FIG. The electrons 20a are used to ionize the gas mixture 2 directly by ionization in the ion trap 10. In this way, the gas mixture 2 to be analyzed can be directly ionized, optionally accumulated and measured in the measuring unit (ion trap 10) without the need to feed the ionized gas mixture into the ion trap 10. Alternatively, the gas mixture 2 can also be ionized directly adjacent to the ion trap 10, wherein in the latter case an ionized gas mixture needs to be delivered to the ion trap 10.
為了產生主離子13a或激發的粒子13b，(中性的)離子化氣體13藉由計量閥15和氣體供應管線16被從氣體貯槽17移出並被供應到電漿源18。離子化氣體13在電漿源18中被離子化或激發，而且藉此產生的離子13a及/或介穩態/激發的粒子13b被供應到離子阱10，以引發氣體混合物2的電荷交換離子化或碰撞離子化。電漿源18可以是射頻電漿源、中頻電漿源、直流電漿源、介電質阻障放電電漿源、大氣壓電漿源、電暈 放電電漿源等。 In order to generate the main ion 13a or the excited particle 13b, the (neutral) ionized gas 13 is removed from the gas storage tank 17 by the metering valve 15 and the gas supply line 16 and supplied to the plasma source 18. The ionized gas 13 is ionized or excited in the plasma source 18, and the ions 13a and/or metastable/excited particles 13b thus generated are supplied to the ion trap 10 to induce charge exchange ions of the gas mixture 2. Ionization or collision ionization. The plasma source 18 can be a radio frequency plasma source, an intermediate frequency plasma source, a direct current plasma source, a dielectric barrier discharge plasma source, an atmospheric piezoelectric slurry source, and a corona. Discharge plasma source, etc.
在本實例中，電漿源18被體現來在低於100℃的溫度下產生離子化氣體13的離子13a及/或介穩態粒子13b，亦即電漿源中的電漿放電在低溫下(在100℃下)發生。舉例來說，這可以藉由施加交變射頻場(頻率在1MHz和30MHz之間)來實現，因為相應的RF放電可以在10℃和200℃之間的溫度下有利地發生，或者可以藉由使用為此特地開發的直流電漿源來實現。可以理解的是，也可以使用能夠將(中性)離子化氣體13轉化或離子化成激發電子態的不同類型離子化裝置來取代電漿源18，以在離子阱10中引發氣體混合物2的碰撞或電荷交換離子化。 In the present example, the plasma source 18 is embodied to generate ions 13a and/or metastable particles 13b of the ionizing gas 13 at a temperature below 100 ° C, that is, the plasma discharge in the plasma source is at a low temperature. (At 100 ° C). This can be achieved, for example, by applying an alternating RF field (frequency between 1 MHz and 30 MHz), since the corresponding RF discharge can advantageously occur at temperatures between 10 ° C and 200 ° C, or This is achieved using a DC plasma source specially developed for this purpose. It will be appreciated that instead of the plasma source 18, a different type of ionization device capable of converting or ionizing the (neutral) ionized gas 13 into an excited electronic state may be used to initiate collision of the gas mixture 2 in the ion trap 10. Or charge exchange ionization.
可以使用複數種氣體和氣體混合物來作為離子化氣體13，例如He、H2、Ar、N2、Xe、Kr、O2等。發現特別有利的是使用鈍氣(特別是氦氣)作為離子化氣體13，該鈍氣被電漿源18轉化成介穩態鈍氣13b，即轉化成鈍氣粒子(例如He*)，該鈍氣粒子是處在正好要離子化之前的激發電子態。特別是可以藉由分析物(即待分析的氣體組分3a、3b)和介穩態鈍氣粒子13b之間的電荷交換來實現特別稀少的(冷的)且具有小碎片分析物的離子化。 A plurality of gases and gas mixtures may be used as the ionizing gas 13, such as He, H 2 , Ar, N 2 , Xe, Kr, O 2 and the like. It has been found to be particularly advantageous to use an blunt gas (especially helium) as the ionizing gas 13 which is converted by the plasma source 18 into a metastable blunt gas 13b, ie into a blunt gas particle (for example He*), which The blunt gas particles are in an excited electronic state just prior to ionization. In particular, particularly rare (cold) ionization with small fragment analytes can be achieved by charge exchange between the analytes (ie the gas components 3a, 3b to be analyzed) and the metastable blunt particles 13b. .
這也使得能夠離子化原子質量數介於100和20 000之間的粒子3b，特別是原子質量數介於20 000和2 000 000之間作為鏈接大分子結構，因為這些鏈接大分子結構不會被介穩態鈍氣粒子13b的冷RF電漿進一步分段。舉例來說，粒子3b可以是大分子的混合物，並具有約0.001-10μm或更大的粒度。或者可以理解的是，離子化氣體(例如氦氣)可以以大致上完全離子化的形式存在(即作為He+)，而且混合的形式也是可能的，例 如使用具有不可忽略比例的He+和He*的離子化氣體。 This also enables the ionization of particles 3b with atomic masses between 100 and 20,000, in particular atomic masses between 20 000 and 2 000 000 as linked macromolecular structures, since these linked macromolecular structures do not The cold RF plasma of the metastable blunt particles 13b is further segmented. For example, the particles 3b may be a mixture of macromolecules and have a particle size of about 0.001 to 10 μm or more. Alternatively, it will be appreciated that ionized gases (e.g., helium) may exist in substantially fully ionized form (i.e., as He + ), and mixed forms are also possible, such as using He + and He with non-negligible proportions. * Ionized gas.
對於在離子阱10中質量數高達2 000 000amu的大粒子3b之粒子量測和特徵化，可以利用待檢測質荷比m/z如以下所述取決於離子阱10中的保存幅值Vrf(軌跡的直徑)和場頻frf的事實：m/z~Vrf/(frf)2。 For the number of particles up to 10 ion trap mass measurement and characterization of large particles 2 of 000 000amu 3b can be detected using a mass to charge ratio m / z save as described below depending on the magnitude of the ion trap 10 V rf (The diameter of the trajectory) and the fact of the field frequency f rf : m/z~V rf /(f rf ) 2 .
因此，可以藉由在離子阱10中增加保存幅值Vrf及/或藉由減小場頻frf來量測質量非常大的粒子3b。 Therefore, the very high quality particles 3b can be measured by increasing the preservation amplitude Vrf in the ion trap 10 and/or by reducing the field frequency frf .
在離子阱10中使用介穩態鈍氣粒子13b(即處在激發電子態的中性粒子)來離子化氣體混合物2的進一步優點包含這些介穩態鈍氣粒子13b的截面特別大的事實，導致在離子阱10中與待分析氣體混合物2之組分碰撞的機率較大。其結果是，待分析的離子化粒子3a、3b可更快被收集在離子阱10的中心，而不需使用為達此目的所要求的較高緩衝氣體壓力。因此，藉由使用介穩態的鈍氣粒子13b來離子化氣體混合物2可以在離子阱10中比已知解決方案明顯更迅速地進行量測，所以可以在每種情況下使用質譜儀1以至少500amu或1000amu的質量帶寬來記錄至少10個光譜/秒。 A further advantage of using the metastable blunt gas particles 13b (i.e., neutral particles in the excited electronic state) to ionize the gas mixture 2 in the ion trap 10 comprises the fact that the cross-section of these metastable blunt particles 13b is particularly large, The probability of colliding with the components of the gas mixture 2 to be analyzed in the ion trap 10 is large. As a result, the ionized particles 3a, 3b to be analyzed can be collected at the center of the ion trap 10 more quickly without using the higher buffer gas pressure required for this purpose. Therefore, ionization of the gas mixture 2 by using the metastable blunt gas particles 13b can be measured significantly more rapidly in the ion trap 10 than known solutions, so the mass spectrometer 1 can be used in each case A mass bandwidth of at least 500 amu or 1000 amu is used to record at least 10 spectra/second.
如以上進一步描述的，特別是也可以使用可以產生電子20a(具有範圍在例如1eV和100eV之間的可變電子能量)的電子束源20來以針對性的方式離子化氣體混合物2中具有特定質荷比的組分3a、3b。可以理解的是，作為圖1所圖示實例的替代例，離子化裝置12可以只有電漿源或只有電子束源20，以在離子阱10中離子化待分析的氣體混合物2。電子20a及/或離子化氣體13的介穩態粒子13b還可以離子化存在於離子阱 10中的殘餘氣體14，即產生殘餘氣體離子14a。 As further described above, it is also possible in particular to use an electron beam source 20 which can generate electrons 20a (having a variable electron energy ranging between, for example, 1 eV and 100 eV) to ionize the gas mixture 2 in a targeted manner. Component 3a, 3b of mass to charge ratio. It will be appreciated that as an alternative to the example illustrated in FIG. 1, the ionization device 12 may have only a plasma source or only an electron beam source 20 to ionize the gas mixture 2 to be analyzed in the ion trap 10. The metastable particles 13b of the electrons 20a and/or the ionized gas 13 may also be ionized in the ion trap The residual gas 14 in 10 produces residual gas ions 14a.
同樣可以在圖1中識別出的是，質譜儀1具有壓力降低單元11，壓力降低單元11被連接到量測室7的入口6，而且壓力降低單元11將量測室7與腔室8的出口4連接。在圖示的實例中，壓力降低單元11具有三個串聯的模組化壓力階段11a-c，用以降低腔室8中待分析氣體混合物2的氣體壓力P0。在圖示的實例中，質譜儀1藉由在腔室8之出口4區域中的凸緣連接。三個壓力階段11a-c各自具有兩個端側的凸緣，藉由該等凸緣可以將三個壓力階段11a-c連接到往量測室7的入口6或連接到其他地方。 It can also be recognized in Fig. 1 that the mass spectrometer 1 has a pressure reduction unit 11, the pressure reduction unit 11 is connected to the inlet 6 of the measurement chamber 7, and the pressure reduction unit 11 connects the measurement chamber 7 to the chamber 8. Exit 4 is connected. In the illustrated example, the pressure reduction unit 11 modular pressure stage 11a-c connected in series with three to be analyzed reduction chamber 8 the gas mixture of the gas pressure P 0 2. In the illustrated example, the mass spectrometer 1 is connected by a flange in the region of the outlet 4 of the chamber 8. The three pressure stages 11a-c each have two end-side flanges by means of which the three pressure stages 11a-c can be connected to the inlet 6 of the measuring chamber 7 or to other places.
取決於應用，即取決於腔室8中氣體混合物2的氣體壓力P0，可以串聯壓力階段11a-c中的一個、兩個或三個或不連接壓力階段來降低到目前為止氣體混合物2可以供應到量測室7中以供分析之用的氣體壓力。這三個壓力階段11a-c被相互協調。舉例來說，在每個壓力階段11a-c中該協調可以藉由係數約100-1000毫巴的壓力降低來實現。在待分析的氣體混合物具有高的氣體壓力P0(100巴-10-2毫巴)的情況下可以使用全部三個壓力階段11a-c，在腔室8中的氣體混合物2具有中度壓力(10-2毫巴-10-5毫巴)的情況下可以使用2個壓力階段11a、11b，而且在腔室8中的氣體混合物2具有低度氣體壓力(<10-5毫巴)的情況下可以只使用1個壓力階段11a或不使用壓力階段，氣體混合物2被輸送通過該等壓力階段。 Depending on the application, ie depending on the gas pressure P 0 of the gas mixture 2 in the chamber 8, one, two or three of the pressure stages 11a-c can be connected in series or not connected to the pressure stage to reduce the gas mixture 2 so far The gas pressure supplied to the measurement chamber 7 for analysis. These three pressure phases 11a-c are coordinated with each other. For example, this coordination can be achieved in each pressure phase 11a-c by a pressure drop of about 100-1000 mbar. All three pressure stages 11a-c can be used in the case where the gas mixture to be analyzed has a high gas pressure P 0 (100 bar - 10 -2 mbar), the gas mixture 2 in the chamber 8 has a moderate pressure In the case of (10 -2 mbar - 10 -5 mbar), two pressure stages 11a, 11b can be used, and the gas mixture 2 in the chamber 8 has a low gas pressure (<10 -5 mbar) In this case, it is possible to use only one pressure stage 11a or no pressure stage, through which the gas mixture 2 is conveyed.
壓力階段11a-c可借助於彼此以氣密方式連接而串聯連接，例如借助於在凸緣上相互旋緊。以此方式，可以非常快速地拆卸或重組壓力階段11a-c，以提供待檢測氣體混合物2的預定壓力範圍的氣體壓力p0，並確保氣體壓力p0在離子阱10的方向上降低到約10-5毫巴或到10-9毫巴， 使得離子阱10可被用於氣體分析。藉由使用一個或更多個壓力階段11a-c，可以使用質譜儀1來分析氣體壓力p0在105毫巴和10-15毫巴之間的氣體混合物2，並具有不變的檢測極限，其中特別是質譜儀1可以以特別簡單的方式適用於所需的壓力範圍。在此，(下)檢測極限可以被定義如下：可以在量測室7中在10-8毫巴的壓力下每秒量測約100個離子。 The pressure stages 11a-c can be connected in series by means of a gas-tight connection to each other, for example by means of a mutual tightening on the flange. In this manner, very quickly detached or recombinant pressure stages 11a-c, the gas mixture to be detected to provide a predetermined pressure range of 2 gas pressure p 0, p 0 and to ensure that the gas pressure is reduced to the ion trap 10 in a direction approximately 10 -5 mbar or to 10 -9 mbar allows the ion trap 10 to be used for gas analysis. By using one or more pressure stages 11a-c, the mass spectrometer 1 can be used to analyze a gas mixture 2 with a gas pressure p 0 between 10 5 mbar and 10 -15 mbar with a constant detection limit In particular, the mass spectrometer 1 can be adapted to the required pressure range in a particularly simple manner. Here, the (lower) detection limit can be defined as follows: About 100 ions can be measured per second in the measurement chamber 7 at a pressure of 10 -8 mbar.
在圖1所示的實例中，離子阱10被體現為磁FT-ICR阱，在下文中將結合圖2更詳細地說明磁FT-ICR阱。在磁FT-ICR阱10中，離子13a陷在均勻的磁場B中，磁場B沿著XYZ坐標系統的Z方向延伸，並迫使陷在FT-ICR阱10中Z方向上的離子13a到達具有質量相關軌域頻率的軌域上。此外，FT-ICR阱10具有交流電場被垂直於磁場B施加並因此產生迴旋共振的配置。在圖示的實例中，該配置具有6個電極21。假使被施加的交流電場之頻率與角迴旋頻率相符，則發生共振而且相關離子13a的迴旋半徑藉由從交流電場取得能量而增加。這些變化導致FT-ICR阱10的電極20上可量測的訊號(其導致電流I)經由放大器22被提供到FFT(快速傅立葉轉換)光譜儀23，FFT光譜儀23同樣是質譜儀1的元件。 In the example shown in FIG. 1, ion trap 10 is embodied as a magnetic FT-ICR well, and the magnetic FT-ICR well will be described in more detail below in connection with FIG . In the magnetic FT-ICR well 10, the ions 13a are trapped in a uniform magnetic field B which extends in the Z direction of the XYZ coordinate system and forces the ions 13a trapped in the Z direction of the FT-ICR well 10 to reach the quality. On the orbital domain of the associated orbital frequency. Further, the FT-ICR well 10 has a configuration in which an alternating electric field is applied perpendicular to the magnetic field B and thus generates a cyclotron resonance. In the illustrated example, this configuration has six electrodes 21. If the frequency of the applied alternating electric field coincides with the angular cyclotron frequency, resonance occurs and the radius of gyration of the associated ion 13a increases by taking energy from the alternating electric field. These changes result in a measurable signal on the electrode 20 of the FT-ICR well 10 (which results in a current I) being supplied via an amplifier 22 to an FFT (Fast Fourier Transform) spectrometer 23, which is also an element of the mass spectrometer 1.
在FFT光譜儀23中接收的、隨時間變化的電流I經受傅立葉轉換，以獲得頻率f相關的質譜圖，該質譜圖被圖示在圖2的右下方。因此，FT-ICR阱10可以直接檢測或直接記錄質譜，使得快速的氣體分析成為可能。也可以從FT-ICR阱10選擇性地去除個別離子或具有特定質量數或質荷比m/z的離子，例如借助被施加到電極21的交流電場來引導所選擇的離子被從阱10移出而抵達不穩定的軌道。 The time-varying current I received in the FFT spectrometer 23 is subjected to Fourier transform to obtain a frequency f-dependent mass spectrum, which is illustrated at the lower right of FIG. Therefore, the FT-ICR well 10 can directly detect or directly record mass spectra, making rapid gas analysis possible. Individual ions or ions having a specific mass or mass to charge ratio m/z can also be selectively removed from the FT-ICR well 10, for example by means of an alternating electric field applied to the electrode 21 to direct the selected ions to be removed from the well 10. And arrived at an unstable track.
同樣可以從圖2識別的是，時間相關的圖像電流I的包線之 振幅在激發後隨著時間降低，其中電流I在時間或瞬間的降低直接相關於平均自由路徑長度，並因此直接相關於FT-ICR阱10中的壓力。若假設電流I的振幅呈指數下降，則有可能在例如時間常數τ的基礎上以高精度測定FT-ICR阱10中的壓力，在時間常數τ期間振幅減少到原始值的1/e(即約37%)的水平；這尤其可以用於測定介穩態粒子的數量(見下文)，因為這個數量與壓力相關。 It can also be identified from Figure 2 that the time-dependent image current I is covered by the envelope. The amplitude decreases with time after excitation, where the decrease in current I in time or moment is directly related to the mean free path length and is therefore directly related to the pressure in the FT-ICR trap 10. If the amplitude of the current I is assumed to decrease exponentially, it is possible to measure the pressure in the FT-ICR well 10 with high precision, for example, based on the time constant τ, and the amplitude is reduced to 1/e of the original value during the time constant τ (ie, A level of about 37%); this can be used in particular to determine the amount of metastable particles (see below), since this amount is related to pressure.
在傅立葉光譜術的幫助下快速記錄質譜不僅可以在上述FT-ICR阱10中發生，而且還可以在圖2所示的阱類型發展中發生。舉例來說，FT-ICR離子阱10可以被體現為所謂的電FT-ICR阱，該電FT-ICR阱包含環形電極和兩個覆蓋電極，射頻高電壓被施加於該環形電極，該兩個覆蓋電極既可作為圖像電荷檢測器亦可作為激發電極。在FT-ICR阱10的緊湊電變型中，離子被保持陷於射頻高電壓。假使離子經歷脈衝激發，則該等離子會在高真空中進行特徵振動，取決於質/荷比(m/z)，該等振動在覆蓋電極由圖像電荷檢測記錄。藉由從兩個覆蓋電極的圖像電荷訊號形成差異來獲得低失真的離子訊號。藉由低雜訊放大器22和光譜儀23來快速傅立葉分析(FFT)離子輸出訊號可以描繪出特徵離子頻率及其強度。頻譜隨後可以被轉換成質譜，其中描繪出檢測到的粒子數目與質荷比m/z相關。 Rapid recording of mass spectra with the help of Fourier spectroscopy can occur not only in the FT-ICR well 10 described above, but also in the development of well types as shown in FIG. For example, the FT-ICR ion trap 10 can be embodied as a so-called electric FT-ICR trap comprising a ring electrode and two cover electrodes to which a radio frequency high voltage is applied, the two The cover electrode can be used both as an image charge detector and as an excitation electrode. In the compact electrical variant of the FT-ICR trap 10, the ions are held trapped in the RF high voltage. If the ions are subjected to pulsed excitation, the ions will undergo characteristic vibrations in a high vacuum, depending on the mass/charge ratio (m/z), which are recorded by the image charge detection at the cover electrode. A low distortion ion signal is obtained by forming a difference from the image charge signals of the two cover electrodes. The fast Fourier analysis (FFT) ion output signal can be used to map the characteristic ion frequency and its intensity by the low noise amplifier 22 and the spectrometer 23. The spectrum can then be converted to a mass spectrum in which the number of detected particles is plotted in relation to the mass to charge ratio m/z.
為了盡可能準確地獲得待分析氣體混合物2或其組分3a、3b的定量分析，也就是為了盡可能精確地測定在特定的質荷比m/z下有多少離子13a存在於離子阱10中，可以進行連續的線上原位質譜儀1校準。在這個過程中，測定主離子(即離子化氣體13的離子13a和殘餘氣體的離子14a)的數量和離子化氣體13的介穩態粒子(可用於在離子阱10中電荷 或碰撞離子化氣體混合物2)的數量13b，因此幾乎可以完全消除由於提供用於離子化的主離子13a、14a或介穩態粒子13b的變化或漂移所產生的時間波動。 In order to obtain as accurately as possible the quantitative analysis of the gas mixture 2 to be analyzed or its components 3a, 3b, that is to say, as accurately as possible, how many ions 13a are present in the ion trap 10 at a specific mass-to-charge ratio m/z A continuous on-line mass spectrometer 1 calibration can be performed. In this process, the amount of the main ion (i.e., the ion 13a of the ionized gas 13 and the ion 14a of the residual gas) and the metastable particle of the ionized gas 13 (which can be used for the charge in the ion trap 10) are measured. Or the number 13b of the ionized gas mixture 2) is impinged, so that time fluctuations due to variations or drifts of the main ions 13a, 14a or the metastable particles 13b for ionization can be almost completely eliminated.
由於特定的量測程序和適當地控制質譜儀1的電子元件，上述的結果是可能的，該控制係由控制裝置19(參見圖1)進行。以下在圖3的基礎上更詳細地說明量測程序的時機，其中指定示例性的持續時間t1到t7用於量測方法的各個步驟。 The above results are possible due to the specific measurement procedure and the proper control of the electronic components of the mass spectrometer 1, which is performed by the control device 19 (see Fig. 1). The timing of the measurement procedure is explained in more detail below on the basis of Fig. 3, wherein exemplary durations t1 to t7 are specified for the various steps of the measurement method.
在第一步驟中(持續時間t1約為1毫秒)，在離子阱10中累積了主離子13a、14a。為了累積的目的，控制裝置19打開計量閥15，並讓離子化氣體13流進電漿源18，在電漿源18中該氣體被離子化並以離子13a的形式進入離子阱10。此外，存在於離子阱10中的殘餘氣體14可以被離子化氣體13的介穩態粒子13b及/或供應到離子阱10的電子20a(部分地)離子化，使得形成殘餘氣體離子14a。 In the first step (duration time t1 is about 1 millisecond), main ions 13a, 14a are accumulated in the ion trap 10. For purposes of accumulation, control device 19 opens metering valve 15 and causes ionized gas 13 to flow into plasma source 18 where it is ionized and enters ion trap 10 in the form of ions 13a. Further, the residual gas 14 present in the ion trap 10 may be (partially) ionized by the metastable particles 13b of the ionized gas 13 and/or the electrons 20a supplied to the ion trap 10, so that the residual gas ions 14a are formed.
一旦離子阱10中累積了足夠數量的主離子13a、14a，則在第二步驟中(持續時間t2約0.01毫秒)藉由激發訊號激發主離子13a、14a，該激發訊號同樣由控制裝置19產生並被施加到離子阱10的相應電極21。在第三步驟中(持續時間t3約為0.1毫秒)量測或檢測離子阱10中的主離子13a、14a之數量。 Once a sufficient number of primary ions 13a, 14a have accumulated in the ion trap 10, the primary ions 13a, 14a are excited by the excitation signal in a second step (lasting t2 about 0.01 milliseconds), which is also generated by the control device 19. And is applied to the corresponding electrode 21 of the ion trap 10. The number of primary ions 13a, 14a in the ion trap 10 is measured or detected in a third step (duration time t3 is about 0.1 milliseconds).
就在第二步驟結束之前和在第三步驟期間，第四步驟(持續時間t4<1毫秒)同時發生，確切地說是從量測室7的入口6輸送(非離子化的)氣體混合物2進入離子阱10，更確切地說是從量測室7的入口6輸送氣體混合物2的氣體脈衝2a進入離子阱10。為了產生氣體脈衝2a，藉由 控制裝置19簡單地致動並打開閥5，閥5打開的持續時間通常在小於約1微秒或小於幾毫秒的區間。控制裝置19將氣體混合物2之氣體脈衝2a的產生與量測主離子13a之數量的步驟同步，其同步方式使得氣體脈衝在主離子13a、14a的數量完成量測時到達離子阱10。視情況，氣體混合物2也可以在直接鄰近離子阱10處被離子化。在這種情況下，氣體脈衝到達離子阱10時有一個時間差，也就是剛好在主離子的數量完成量測之後。由於氣體脈衝2a往離子阱10的入口移動，視情況地可以不用提供輸送裝置來將離子化的氣體混合物2輸入離子阱10。 Just before the end of the second step and during the third step, the fourth step (duration t4 < 1 millisecond) occurs simultaneously, specifically from the inlet 6 of the measuring chamber 7 (non-ionized) gas mixture 2 Entering the ion trap 10, more specifically the gas pulse 2a of the gas mixture 2 from the inlet 6 of the measuring chamber 7, enters the ion trap 10. In order to generate the gas pulse 2a, The control device 19 simply actuates and opens the valve 5, which is typically open for a duration of less than about 1 microsecond or less. The control means 19 synchronizes the generation of the gas pulse 2a of the gas mixture 2 with the step of measuring the number of main ions 13a in such a manner that the gas pulse reaches the ion trap 10 when the number of main ions 13a, 14a is measured. The gas mixture 2 can also be ionized directly adjacent to the ion trap 10, as appropriate. In this case, there is a time difference when the gas pulse reaches the ion trap 10, that is, just after the amount of main ions is measured. As the gas pulse 2a moves toward the inlet of the ion trap 10, it is optionally possible to supply the ionized gas mixture 2 to the ion trap 10 without providing a delivery device.
為了便於氣體混合物2或氣體脈衝從腔室8流入離子阱10，可以在閥5的區域、在腔室8的出口4的區域、在進入量測室7的入口6的區域及/或在入口6和離子阱10之間的區域設置例如風扇類型的輸送裝置。為了將氣體混合物2或氣體脈衝輸送到離子阱10的目地，量測室7也可以被連接到泵送裝置(圖1中未圖示)。 In order to facilitate the flow of gas mixture 2 or gas pulses from the chamber 8 into the ion trap 10, it may be in the region of the valve 5, in the region of the outlet 4 of the chamber 8, in the region of the inlet 6 into the measuring chamber 7, and/or at the inlet. The area between 6 and the ion trap 10 is provided, for example, of a fan type of conveying device. In order to deliver the gas mixture 2 or gas pulses to the destination of the ion trap 10, the measurement chamber 7 can also be connected to a pumping device (not shown in Figure 1).
在第五步驟中(持續時間t5約為0.1毫秒)，以氣體脈衝2a輸送的氣體混合物2在離子阱10中藉由碰撞離子化及/或藉由電荷交換離子化由主離子13a、14a或介穩態粒子13b進行離子化。在這個過程中發現的是，假使離子化氣體13或離子化氣體13的離子13a和介穩態粒子13b的流動方向與氣體脈衝2a的流動方向相反是有利的，使得離子化氣體13的流動和氣體脈衝2a在離子阱10的內部互相碰撞。為了達到這個目的，如圖1所示，假使供應氣體脈衝2a的入口6和供應離子化氣體13之氣流的離子化裝置12的入口被設置成彼此相對是有利的。這同樣適用於電子源20或電子束20a，電子源20或電子束20a同樣應對齊氣體脈衝2a或應被設置 在用於供應氣體脈衝2a的入口6之相對處，如圖1所繪示。 In a fifth step (duration time t5 is about 0.1 milliseconds), the gas mixture 2 transported by the gas pulse 2a is ionized by collision in the ion trap 10 and/or ionized by charge exchange by the main ions 13a, 14a or The metastable particles 13b are ionized. It is found in this process that it is advantageous that the flow direction of the ion 13a and the metastable particle 13b of the ionized gas 13 or the ionized gas 13 is opposite to the flow direction of the gas pulse 2a, so that the flow of the ionized gas 13 is The gas pulses 2a collide with each other inside the ion trap 10. In order to achieve this, it is advantageous to provide the inlets of the ionizing means 12 for supplying the gas pulse 2a and the inlet of the ionizing means 12 for supplying the ionizing gas 13 to each other as shown in Fig. 1. The same applies to the electron source 20 or the electron beam 20a, the electron source 20 or the electron beam 20a should also be aligned with the gas pulse 2a or should be set The opposite of the inlet 6 for supplying the gas pulse 2a is as shown in FIG.
在隨後的第六步驟中(持續時間t6約1ms)，氣體混合物2的離子被激發。在激發氣體混合物2的離子之前或過程中，可以憑藉產生並被施加到電極20的適當激發訊號來移除或抑制離子阱10中的主離子13a、14a。在隨後的第七步驟中(持續時間t7=高達100毫秒)，量測或檢測氣體混合物2的激發離子或離子化組分3a、3b，其中所量測的訊號位準Hf正比於在相應質荷比m/z中各別離子群體的離子數。 In the subsequent sixth step (duration time t6 about 1 ms), the ions of the gas mixture 2 are excited. The main ions 13a, 14a in the ion trap 10 may be removed or suppressed by an appropriate excitation signal generated and applied to the electrode 20 before or during the excitation of the ions of the gas mixture 2. In a subsequent seventh step (t7 = duration of up to 100 ms), the measurement or detection of a gas mixture excited or ionized ions of component 3a 2, 3b, wherein the measured signal level is proportional to the corresponding H f The number of ions in each ion population in the mass-to-charge ratio m/z.
為了最小化時間相關的波動對提供用於離子化的主離子13a、14a之數量或測定離子數Hf的介穩態粒子13b的影響，採用以下的程序：對於每個頻率f或每個質荷比m/z，訊號位準Hf係由以下的表達式決定：Hf(校正)=K * Hf(未校正)*H1/ΣHf, (1)，其中H1表示在離子阱中被穩定保存和激發的所有離子之訊號位準，Hf(未校正)表示感興趣的離子或待分析的離子化組分3a、3b之頻譜位準或訊號位準，ΣHf表示存在於量測光譜中的光譜線之所有訊號位準的總和，以及K表示與質量和頻率無關的校正因子，其包括提供用於離子化的主離子13a、14a或確切的說為介穩態粒子13b之測定數目，其方式為較大的測定數目帶來較小的校正係數K，反之亦然。應當理解的是，在離子化氣體13大體上以介穩態粒子13b(例如He*)的形式存在的情況下通常足以測定介穩態粒子13b的數量，而且在離子化氣體13大體上以主粒子13a(例如He+)的形式存在的情況下通常足以測定用於校準的數量。 To minimize time-dependent fluctuations of the metastable particles are provided for ionization ion main 13a, 14a of or determining the amount of ions 13b of the f H, the following procedure: for each frequency or each mass f The charge ratio m/z, the signal level H f is determined by the following expression: H f (correction) = K * H f (uncorrected) * H1/ΣH f, (1), where H1 is represented in the ion trap The signal level of all ions that are stably stored and excited, H f (uncorrected) indicates the spectral level or signal level of the ion of interest or the ionized component 3a, 3b to be analyzed, and ΣH f indicates the amount present in the amount Measuring the sum of all signal levels of the spectral lines in the spectrum, and K representing a quality and frequency independent correction factor, including providing the primary ions 13a, 14a or, specifically, the metastable particles 13b for ionization. The number is determined in such a way that a larger number of measurements results in a smaller correction factor K and vice versa. It should be understood that in the case where the ionized gas 13 is substantially present in the form of metastable particles 13b (e.g., He*), it is generally sufficient to determine the amount of metastable particles 13b, and in the ionized gas 13 is substantially the main The presence of the form of particles 13a (e.g., He + ) is generally sufficient to determine the amount used for calibration.
藉由檢測量測電極21上的感應訊號之位準Hf，乘以在離子 阱中穩定保存和激發的全部離子13a、14a之激發度或數量H1，並考量校正因子K，可以以具有高精度的預定質荷比決定位在離子阱10中的氣體混合物2的離子化組分3a、3b之實際數目，即通常具有小於5%的不準確度。激發度表示雲霄飛車式移動的半徑對離子單元的芯半徑之比。對於任何選定的氣體種類，上述校準可以在任何時候進行，特別是可以在實際量測期間的任何時候進行。 By detecting the level H f of the sensing signal on the measuring electrode 21, multiplying the excitation or quantity H1 of all the ions 13a, 14a stably stored and excited in the ion trap, and considering the correction factor K, it can be high The predetermined predetermined mass-to-charge ratio determines the actual number of ionized components 3a, 3b of the gas mixture 2 in the ion trap 10, i.e., typically has an inaccuracy of less than 5%. The degree of excitation represents the ratio of the radius of the roller coaster movement to the core radius of the ion unit. The calibration described above can be performed at any time for any selected gas species, particularly at any time during the actual measurement period.
原則上，以上所說明的程序可以被重複多次或任何次數。然而，假使在氣體混合物2離子化之後，氣體混合物2的離子化組分3a、3b在離子阱10中被重複激發可以是有利的，而不用在程序中再離子化氣體混合物2，如下面在圖4的基礎上描述的。 In principle, the procedure described above can be repeated multiple times or any number of times. However, if the ionization components 3a, 3b of the gas mixture 2 are repeatedly excited in the ion trap 10 after ionization of the gas mixture 2, it may be advantageous to re-ionize the gas mixture 2 in the process, as in Figure 4 is based on the description.
圖4圖示量測離子阱10中的氣體混合物2之離子化組分3a、3b的說明，其中在碰撞或電荷交換離子化完成之後，在時間t0使用脈衝激發訊號SA來幫助激發(視需要一次到幾十次)氣體混合物2之離子化組分3a、3b，在圖4中以「I」表示。在每個激發期間或之後記錄在固定的時段△Tm1至△Tmx(約5ms或更短)間的質譜MS1到MSx(在本實例中)。換句話說，預定的量測窗口(具有恆定的持續時間)被重複移動，以在幾個連續的激發期間分別記錄質譜MS1到MSx，而不需要進一步的離子化。 Gas 10 Figure 4 illustrates the measurement of the ion trap ionization mixture of components 3a 2, 3b description, wherein after the charge exchange or ionizing collisions is completed, at time t 0 using a pulsed excitation signal to help stimulate the SA (as The ionization components 3a, 3b of the gas mixture 2 are required to be used once to several tens of times, and are indicated by "I" in FIG. Mass spectra MS1 to MSx (in this example) between fixed periods ΔTm1 to ΔTmx (about 5 ms or shorter) are recorded during or after each excitation. In other words, the predetermined measurement window (having a constant duration) is repeatedly moved to separately record the mass spectra MS1 to MSx during several consecutive excitations without further ionization.
這使得可以非常快速地進行位於離子阱10中的氣態組分3a、3b之質譜分析，結果可以實時觀察在量測過程中進行的化學製程。特別是，可以在分析物分子相互反應之前量測分析物分子，而且可以檢測在化學反應過程中形成的中間產物。應用上述量測原理的質譜儀1尤其適用於化學製程分析。 This makes it possible to carry out mass spectrometry of the gaseous components 3a, 3b located in the ion trap 10 very quickly, with the result that the chemical process carried out during the measurement can be observed in real time. In particular, the analyte molecules can be measured before the analyte molecules react with one another, and the intermediate products formed during the chemical reaction can be detected. The mass spectrometer 1 applying the above measurement principle is particularly suitable for chemical process analysis.
為了增加動態範圍，即質譜儀1的最大可檢測訊號強度與最小可檢測訊號強度之間的比率，可以如下所述在圖5a和圖5b的基礎上評估質譜。 To increase the dynamic range, i.e., the ratio between the maximum detectable signal intensity of the mass spectrometer 1 and the minimum detectable signal strength, the mass spectrum can be evaluated on the basis of Figures 5a and 5b as described below.
圖5a圖示其中有所謂用於提高動態響應的SWIFT激發的質譜圖，其中相對大的離子群，即其中在給定質荷比m/z的粒子數超過預定閾值SW的離子群(參見圖5a)，在量測過程中被從離子阱10移出或抑制。特別是，SWIFT激發可以被用來實現梳狀濾波器，其中每個對應於不同量測區域MB1至MBx(即對應於幾個質荷比區間)的離子群之幾個亞群被同時量測，如圖5a所示。 Figure 5a illustrates a mass spectrum in which there is a so-called SWIFT excitation for increasing the dynamic response, wherein a relatively large population of ions, i.e., an ion population in which the number of particles at a given mass-to-charge ratio m/z exceeds a predetermined threshold SW (see figure) 5a) is removed or suppressed from the ion trap 10 during the measurement process. In particular, SWIFT excitation can be used to implement a comb filter in which several subgroups of ion groups corresponding to different measurement regions MB1 to MBx (ie corresponding to several mass-to-charge ratio intervals) are simultaneously measured. As shown in Figure 5a.
也可以藉由切換量測區域來增加動態響應，如圖5b所繪示。在圖5b中，質譜被分成量測區域MB1至MBx，而且在每種情況下具有不同的質荷比，其中每個量測區域MB1至MBx是在不同的量測時間t1到tx評估。同樣可以藉由量測範圍MB1至MBx之間的這種時間切換或藉由以此方式實現的質量選擇性時間多工量測來增加動態範圍。 It is also possible to increase the dynamic response by switching the measurement area, as shown in Figure 5b. In Fig. 5b, the mass spectrum is divided into measurement areas MB1 to MBx, and in each case have different mass-to-charge ratios, wherein each of the measurement areas MB1 to MBx is evaluated at different measurement times t1 to tx. The dynamic range can also be increased by such time switching between the measurement ranges MB1 to MBx or by mass selective time multiplex measurement achieved in this way.
可以理解的是，也可以將結合圖5a和圖5b所描述的量測模式組合，以提高動態範圍。也可以使用比本文所述更複雜的量測方法類型，以進一步增加動態範圍。當使用了結合圖5a和圖5b所描述的兩種量測原理中之一種時，可以視情況地能夠實現108：1或更大的質譜儀1的動態範圍。 It will be appreciated that the measurement modes described in connection with Figures 5a and 5b can also be combined to increase the dynamic range. It is also possible to use a more complex type of measurement method than described herein to further increase the dynamic range. When one of the two measurement principles described in connection with Figures 5a and 5b is used, the dynamic range of the mass spectrometer 1 of 10 8 : 1 or greater can be achieved as appropriate.
可以將在離子阱10中累積氣體混合物2的個別離子化氣體組分的選擇與上述量測方法組合使用來增加動態範圍，以降低質譜儀的檢測極限。這裡所使用的是離子阱質譜儀在不連續的基礎上操作，而且離子 數的分析只在預定的累積時間(例如少於約5毫秒)之後進行。藉由將上述用於提高動態響應的方法(SWIFT或時間多工量測，參見圖5a和圖5b)與離子阱10的累積能力組合，能夠累積個別的離子直到存在足夠大的量測訊號。在已知(校準的)量測訊號和已知累積時間的情況下，待分析離子群體可以被定量測定。以這種方式，可以降低質譜儀的檢測極限到10-15毫巴或更小。 The selection of individual ionized gas components that accumulate gas mixture 2 in ion trap 10 can be used in combination with the above described measurement methods to increase the dynamic range to reduce the detection limit of the mass spectrometer. As used herein, an ion trap mass spectrometer operates on a discontinuous basis, and the analysis of the number of ions is performed only after a predetermined accumulation time (e.g., less than about 5 milliseconds). By combining the above-described method for improving dynamic response (SWIFT or time multiplex measurement, see Figs. 5a and 5b) with the accumulation capability of the ion trap 10, individual ions can be accumulated until there is a sufficiently large measurement signal. In the case of known (calibrated) measurement signals and known accumulation times, the population of ions to be analyzed can be quantified. In this way, the detection limit of the mass spectrometer can be reduced to 10 -15 mbar or less.
除了上述的離子阱類型之外，也可以在質譜儀1中使用其它類型的離子阱，該等離子阱能夠三維保存或累積離子及藉由傅立葉轉換進行評估，例如潘寧阱(Penning trap)、環形阱(toroidal trap)、保羅阱(Paul trap)、線性阱、軌域阱(orbitrap)、EBIT及RF聚束器。 In addition to the ion trap type described above, other types of ion traps can be used in the mass spectrometer 1, which can store or accumulate ions in three dimensions and be evaluated by Fourier transform, such as Penning trap, ring Toroidal trap, Paul trap, linear trap, orbitrap, EBIT, and RF buncher.
上述質譜儀1可以在各個應用領域中找到用途。除了化學製程分析之外(此已結合圖4被描述為可能的應用)，質譜儀1可以例如被用在EUV微影術中，EUV微影術係用於分析EUV系統(例如EUV微影設備)中的殘餘氣體，以測定其中存在的殘餘氣體氛圍中的污染物質濃度或量。 The mass spectrometer 1 described above can find use in various fields of application. In addition to chemical process analysis (which has been described as a possible application in connection with Figure 4), mass spectrometer 1 can be used, for example, in EUV lithography, which is used to analyze EUV systems (eg EUV lithography equipment). Residual gas in the process to determine the concentration or amount of contaminant in the atmosphere of the residual gas present therein.
圖6示意性圖示這樣的EUV微影設備101。EUV微影設備101包含被容置在獨立的真空殼體中並依序被配置在由EUV光源105產生的EUV輻射106之光束路徑上的輻射產生系統102、照明系統103及投影系統104，該光束路徑從輻射產生系統102的EUV光源105出發。舉例來說，電漿源或同步加速器可作為EUV光源105。從EUV光源105射出、在約5nm和約20nm之間的波長範圍中的輻射首先集中在準直器107。在下游單色器108的幫助之下，藉由改變入射角來濾出所需的操作波長λB(在 本實例中約13.5nm)，如雙箭頭所示。準直器107和單色器108被體現為反射光學元件。 FIG. 6 schematically illustrates such an EUV lithography apparatus 101. The EUV lithography apparatus 101 includes a radiation generating system 102, an illumination system 103, and a projection system 104 that are housed in separate vacuum housings and sequentially disposed on the beam path of EUV radiation 106 generated by the EUV source 105. The beam path originates from the EUV source 105 of the radiation generating system 102. For example, a plasma source or synchrotron can be used as the EUV source 105. Radiation emitted from the EUV source 105 in the wavelength range between about 5 nm and about 20 nm is first concentrated on the collimator 107. With the aid of the downstream monochromator 108, the desired operating wavelength λ B (about 13.5 nm in this example) is filtered out by varying the angle of incidence, as indicated by the double arrow. Collimator 107 and monochromator 108 are embodied as reflective optical elements.
在輻射產生系統102中針對波長和空間分佈進行處理的EUV輻射被引入照明系統103，照明系統103具有第一和第二反射光學元件109、110(反射鏡)。兩個反射光學元件109、110將輻射導向光罩111，光罩111作為進一步的反射光學元件，並具有以縮小比例被投影系統104成像在晶圓112上的結構。為此目的，在投影系統104中設置第三和第四反射光學元件113、114(反射鏡)。 EUV radiation processed in the radiation generating system 102 for wavelength and spatial distribution is introduced into the illumination system 103, which has first and second reflective optical elements 109, 110 (mirrors). The two reflective optical elements 109, 110 direct radiation to the reticle 111, which acts as a further reflective optical element and has a structure that is imaged onto the wafer 112 by the projection system 104 in a reduced scale. For this purpose, third and fourth reflective optical elements 113, 114 (mirrors) are provided in projection system 104.
反射光學元件109、110、111、113、114各具有曝露於光源105之EUV輻射106的光學表面。光學元件109、110、111、113、114分別在輻射產生系統102的殘餘氣體氛圍102a、照明系統103的殘餘氣體氛圍103a及投影系統104的殘餘氣體氛圍104a中的真空條件下操作，其中該等殘餘氣體氛圍通常含有小部分的空氣、氫氣(H2)及/或氦(He)以及視情況的其他殘餘氣體。由於EUV微影設備1的內部不能進行烘烤，故無法完全避免不良的污染組分存在於各個殘餘氣體氛圍102a、103a、104a中。 The reflective optical elements 109, 110, 111, 113, 114 each have an optical surface that is exposed to the EUV radiation 106 of the source 105. The optical elements 109, 110, 111, 113, 114 operate under vacuum conditions in the residual gas atmosphere 102a of the radiation generating system 102, the residual gas atmosphere 103a of the illumination system 103, and the residual gas atmosphere 104a of the projection system 104, respectively. The residual gas atmosphere typically contains a small portion of air, hydrogen (H 2 ) and/or helium (He) and optionally other residual gases. Since the inside of the EUV lithography apparatus 1 cannot be baked, it is impossible to completely prevent the occurrence of undesirable contamination components in the respective residual gas atmospheres 102a, 103a, 104a.
在EUV微影設備1的操作過程中，包含真空泵115的真空產生單元產生的殘餘氣體氛圍104a通常在投影系統104中具有大於10-5毫巴的整體壓力。真空或殘餘氣體氛圍103a、102a也可以相應地被產生在照明系統103或在輻射產生系統102中。 During operation of the EUV lithography apparatus 1, the residual gas atmosphere 104a produced by the vacuum generating unit including the vacuum pump 115 typically has an overall pressure in the projection system 104 of greater than 10 -5 mbar. Vacuum or residual gas atmospheres 103a, 102a may also be generated in illumination system 103 or in radiation generation system 102, respectively.
為了測定投影系統104的殘餘氣體氛圍104a中整體污染物質及/或個別的每種污染物質之比例，特別是在第二反射鏡114的附近，藉由凸緣將質譜儀1連接到投影系統104，質譜儀1具有如上面進一步描述的 設計，即質譜儀1具有入口6，以將位在投影系統104中的殘餘氣體混合物直接引入離子阱10，即不需先前的離子化，離子阱10作為量測單元並被配置在量測室7中，以藉由例如電荷交換或碰撞離子化來離子化該氣體。 In order to determine the proportion of overall contaminants and/or individual contaminants in the residual gas atmosphere 104a of the projection system 104, particularly in the vicinity of the second mirror 114, the mass spectrometer 1 is coupled to the projection system 104 by a flange. , mass spectrometer 1 has as described further above The design, ie the mass spectrometer 1 has an inlet 6 to introduce the residual gas mixture in the projection system 104 directly into the ion trap 10, ie without prior ionization, the ion trap 10 as a measuring unit and arranged in the measuring chamber In 7, the gas is ionized by, for example, charge exchange or collision ionization.
入口6在投影系統104的殘餘氣體氛圍104a和質譜儀1之間形成真空連接。入口6(即真空連接(真空管))具有小於100mm的橫截面A，較佳小於5mm，特別是小於1mm。如圖1所示，質譜儀1可以具有一個或多個站，以確保殘餘氣體壓力往離子阱10降低到<10-5毫巴，使得傳統的殘餘氣體分析儀可被用於殘餘氣體分析。 The inlet 6 forms a vacuum connection between the residual gas atmosphere 104a of the projection system 104 and the mass spectrometer 1. The inlet 6 (i.e. vacuum connection (vacuum tube)) has a cross section A of less than 100 mm, preferably less than 5 mm, in particular less than 1 mm. As shown in Figure 1, the mass spectrometer 1 can have one or more stations to ensure that the residual gas pressure is reduced to <10 -5 mbar to the ion trap 10, allowing conventional residual gas analyzers to be used for residual gas analysis.
同樣可以在圖6中確定的是，第二反射鏡114和質譜儀1的連接位置PS(在真空連接或入口6的中間形成在投影光學單元104的殼體上)之間的距離D小於50cm。這是有利的，因為能夠盡可能精確地檢測存在於第二反射鏡114附近(更精確是在其光學表面附近)的污染物質的部分或分壓。在質譜分析期間，特別的是可以量測或檢測以下污染物質或其混合物中之至少一者：氧氣(O2)、臭氧(O3)、水(H2O)、CXHYOZ(通常高達10Mamu)，及金屬-CXHYOZ化合物(通常高達10Mamu)。 It can also be determined in Fig. 6 that the distance D between the second mirror 114 and the connection position P S of the mass spectrometer 1 (formed on the housing of the projection optical unit 104 in the middle of the vacuum connection or inlet 6) is smaller than 50cm. This is advantageous because it is possible to detect as much as possible the partial or partial pressure of contaminants present in the vicinity of the second mirror 114, more precisely in the vicinity of its optical surface. During mass spectrometry, it is particularly possible to measure or detect at least one of the following contaminants or mixtures thereof: oxygen (O 2 ), ozone (O 3 ), water (H 2 O), C X H Y O Z (usually up to 10 Mamu), and metal-C X H Y O Z compounds (usually up to 10 Mamu).
另外地或替代地，其他的質譜儀或質譜儀1可以被設置在照明系統103的連接位置PB，連接位置PB與設置在照明系統103中的反射鏡109、110(例如第一反射鏡109)的距離D小於50cm。 Additionally or alternatively, other mass spectrometers or mass spectrometers 1 may be provided at the connection location P B of the illumination system 103, the connection location P B and the mirrors 109, 110 (eg the first mirror) provided in the illumination system 103 109) The distance D is less than 50 cm.
因此，質譜儀1或其他的質譜儀可以被設置在輻射產生系統102中的第一連接位置PL1，第一連接位置PL1被設在與通道開口116的距離小於1m處，較佳為小於50cm，通道開口116用於讓EUV輻射106通過而進入照明系統103。質譜儀1也可以位在第二連接位置PL2，第二連接 位置PL2被設在距離收集器107(通常是處在收集器反射鏡的形式)的相應距離D小於100cm、較佳為小於50cm處，或被設在第三連接位置PL3，第三連接位置PL3被設在與EUV光源105的距離小於100cm、較佳為小於50cm處。以上述的方式可以以高精度測定在各個光學元件114、109、116、107附近或在EUV光源105附近的污染水平。 Therefore, the mass spectrometer 1 or other mass spectrometer can be disposed at the first connection position P L1 in the radiation generating system 102, and the first connection position P L1 is set at a distance from the channel opening 116 of less than 1 m, preferably less than 50 cm, the passage opening 116 is used to pass the EUV radiation 106 into the illumination system 103. The mass spectrometer 1 can also be located at a second connection position P L2 , the second connection position P L2 being set at a distance D from the collector 107 (typically in the form of a collector mirror) of less than 100 cm, preferably less than At 50 cm, or at the third connection position P L3 , the third connection position P L3 is set at a distance from the EUV light source 105 of less than 100 cm, preferably less than 50 cm. The level of contamination in the vicinity of each of the optical elements 114, 109, 116, 107 or in the vicinity of the EUV source 105 can be measured with high precision in the manner described above.
圖7示意性圖示用於在基板202(在此案例中：矽晶圓)上進行原子層沉積的裝置201，基板202被放在製程室205(反應室)內部204的架座203上。架座203和製程室205的壁都可被加熱到(視情況不同的)溫度。架座203可以被連接到馬達，以在塗佈期間將基板202置入旋轉運動中。裝置201還包含容器206，容器206中容置金屬有機前驅物材料，在本實例中，該金屬有機前驅物材料為肆(乙基甲基胺基)鉿(tetrakis(ethylmethylamino)hafnium，TEMAH)或另一種金屬有機前驅物。為了將前驅物材料從容器206移到製程室205，使用了惰性載氣，例如氬氣或氫氣，該惰性載氣可以藉由可控閥207供應到容器206。另一個容器208用以提供臭氧氣體O3或另一種摻雜氣體作為原子層沉積中的反應物。 FIG. 7 schematically illustrates an apparatus 201 for atomic layer deposition on a substrate 202 (in this case: a germanium wafer) that is placed on a mount 203 of the interior 204 of a process chamber 205 (reaction chamber). Both the mount 203 and the walls of the process chamber 205 can be heated to (as the case may be) temperatures. The mount 203 can be coupled to a motor to place the substrate 202 into rotational motion during coating. The device 201 further includes a container 206 in which the metal organic precursor material is contained. In the present example, the metal organic precursor material is tetrakis (ethylmethylamino) hafnium (TEMAH) or Another metal organic precursor. To move the precursor material from the vessel 206 to the process chamber 205, an inert carrier gas, such as argon or hydrogen, is used, which may be supplied to the vessel 206 by a controllable valve 207. Another vessel 208 for supplying ozone gas O 3 as the dopant gas, or another atomic layer deposition reactants.
在每種情況下，帶有前驅物和摻雜氣體(例如臭氧氣體)的載氣可以被處在可控閥209a、209b形式的可控入口引入製程室205。分配器歧管210被設置在腔室205中，以朝基板202的方向上盡可能均勻地分配進入的氣體。藉由可控閥209a、209b也可以供應淨化氣體(例如氬氣)到製程室205，以淨化製程室205和各別的供應管線。另一個形成氣體出口的可控閥211被連接到真空泵212，以從製程室205移除氣體。為了監測製程室205中的殘餘氣體氛圍，質譜儀1被設置在氣體處置系統213的真空 管線中的納入位置EE，氣體處置系統213形成在出口閥211的下游，準確地說是直接在真空泵212的上游。也可以將質譜儀1附加於真空泵212下游的氣體處置系統213的排氣管線中的納入位置EG。 In each case, a carrier gas with a precursor and a dopant gas (e.g., ozone gas) can be introduced into the process chamber 205 in the form of a controllable inlet in the form of a controllable valve 209a, 209b. A distributor manifold 210 is disposed in the chamber 205 to distribute the incoming gas as evenly as possible toward the substrate 202. A purge gas (e.g., argon) may also be supplied to the process chamber 205 via the controllable valves 209a, 209b to purge the process chamber 205 and the respective supply lines. Another controllable valve 211 forming a gas outlet is connected to vacuum pump 212 to remove gas from process chamber 205. In order to monitor the residual gas atmosphere in the process chamber 205, the mass spectrometer 1 is placed in the infusion position E E in the vacuum line of the gas treatment system 213, and the gas treatment system 213 is formed downstream of the outlet valve 211, specifically directly in the vacuum pump Upstream of 212. It is also possible to attach the mass spectrometer 1 to the incorporation position E G in the exhaust line of the gas treatment system 213 downstream of the vacuum pump 212.
另外地或替代地，質譜儀1也可以被形成在氣體供應系統216中的納入位置EA、EB，用於例如在相應的供應管線216a、216b中供應反應物到製程室205。另外，或作為替代，質譜儀1還可以被整合在氣體混合系統215的納入位置EC，即在形成於兩個供應管線216a、216b的會合點下游的供應管線中。後者是有利的，因為在此處描述的塗佈製程中兩個供應管線216a、216b不會被同時使用來供應氣體到製程室205。在分配器歧管210中的納入位置ED也是可以的，其中在這種情況下納入位置ED較佳與製程室205間隔小於1m的距離D，特別是小於50cm。另外，或作為替代，質譜儀1或其他的質譜儀和1也可以被附接於製程室205殼體上的納入位置EF，如結合圖6所述。 Additionally or alternatively, mass spectrometer 1 may also be formed at incorporation locations E A , E B in gas supply system 216 for supplying reactants to process chamber 205, for example, in respective supply lines 216a, 216b. Additionally, or alternatively, a mass spectrometer can also be integrated in the supply line 215 into a gas mixing system position E C, i.e. formed in the downstream junction point of the two supply lines 216a, 216b of the. The latter is advantageous because the two supply lines 216a, 216b are not used simultaneously to supply gas to the process chamber 205 during the coating process described herein. The inclusion position E D in the distributor manifold 210 is also possible, wherein in this case the inclusion position E D is preferably spaced from the process chamber 205 by a distance D of less than 1 m, in particular less than 50 cm. Additionally or alternatively, mass spectrometer 1 or other mass spectrometers and 1 may also be attached to the incorporation location E F on the housing of process chamber 205 as described in connection with FIG.
質譜儀1用於檢測或測定腔室205的殘餘氣體氛圍中所含的(納入位置EF)、腔室205中將含的(製程室205上游的納入位置EA、EB、EC、ED)或腔室205中已含的(製程室205下游的納入位置EE、EG)至少一種氣態組分的分壓量。如在設置於氣體處置系統213中的質譜儀1之基礎上所示，該質譜儀具有離子阱10，其中待分析的氣體或氣體混合物可以藉由例如電荷交換或碰撞離子化進行離子化。為了將離子化氣體組分的氣流帶入離子阱10中，質譜儀1可以被連接到真空泵(未圖示)。保存在離子阱10中的離子可以在離子阱10中直接進行檢測。 The mass spectrometer 1 is used to detect or measure (incorporate position E F ) contained in the residual gas atmosphere of the chamber 205, and to include in the chamber 205 (inclusion positions E A , E B , E C upstream of the process chamber 205, E D ) or a partial pressure of at least one gaseous component contained in the chamber 205 (inclusion locations E E , E G downstream of the process chamber 205 ). As shown on the basis of the mass spectrometer 1 provided in the gas treatment system 213, the mass spectrometer has an ion trap 10 in which the gas or gas mixture to be analyzed can be ionized by, for example, charge exchange or collision ionization. In order to bring the gas stream of the ionized gas component into the ion trap 10, the mass spectrometer 1 can be connected to a vacuum pump (not shown). The ions held in the ion trap 10 can be directly detected in the ion trap 10.
為了將氧化鉿(HfO2)的塗層214施加於基板202上，進 行以下的程序：首先將帶有TEMAH前驅物的載氣經由第一閥209a供應到製程室205。然後，切換第一閥209a並藉由第一閥209a將淨化氣體供應到製程室205(參見箭頭)，而後者連同載氣或前驅物的殘餘物則藉由真空泵212抽出通過打開的出口閥211。淨化之後，出口閥211被關閉，而臭氧或摻雜氣體則經由第二閥209b被引入腔室205，該臭氧或摻雜氣體在基板202的曝露表面上與前驅物進行化學反應。接著，藉由淨化氣體來淨化腔室205，淨化氣體經由第二閥209b(參見箭頭)被供應到腔室，並在出口閥211打開時連同臭氧或摻雜氣體殘餘物或可能形成的反應產物被真空泵212抽出。在上述的程序中，由氧化鉿製成的單層被沉積在基板202上。關閉出口閥211之後，此程序可被重複數次，準確地說是直到HfO2塗層214已經達到所需厚度d。 In order to apply the coating 214 of hafnium oxide (HfO 2 ) to the substrate 202, the following procedure is performed: First, a carrier gas with a TEMAH precursor is supplied to the process chamber 205 via the first valve 209a. Then, the first valve 209a is switched and the purge gas is supplied to the process chamber 205 (see arrow) by the first valve 209a, and the latter, together with the residue of the carrier gas or precursor, is withdrawn through the open outlet valve 211 by the vacuum pump 212. . After purification, the outlet valve 211 is closed and ozone or doping gas is introduced into the chamber 205 via a second valve 209b that chemically reacts with the precursor on the exposed surface of the substrate 202. Next, the chamber 205 is purged by purge gas, which is supplied to the chamber via a second valve 209b (see arrow) and together with ozone or dopant gas residues or possible reaction products when the outlet valve 211 is opened It is taken out by the vacuum pump 212. In the above procedure, a single layer made of yttrium oxide is deposited on the substrate 202. After the outlet valve 211 is closed, this procedure can be repeated several times, precisely until the HfO 2 coating 214 has reached the desired thickness d.
供應帶有前驅物的載氣的持續時間、供應臭氧或摻雜氣體的持續時間及淨化程序的持續時間通常在幾秒的範圍中。控制裝置215用於致動閥207、209a、209b、211，以便在沉積製程的上述步驟之間進行切換。可以理解的是，控制裝置215不僅可以在打開位置和關閉位置之間切換閥207、209a、209b、211，而且還可以視情況地藉由電子控制裝置215來控制流過各個閥207、209a、209b、211的質量流量。 The duration of supply of the carrier gas with the precursor, the duration of the supply of ozone or doping gas, and the duration of the purification process are typically in the range of a few seconds. Control device 215 is used to actuate valves 207, 209a, 209b, 211 to switch between the above steps of the deposition process. It can be understood that the control device 215 can switch not only the valves 207, 209a, 209b, 211 between the open position and the closed position, but also can be controlled by the electronic control device 215 to flow through the respective valves 207, 209a, Mass flow of 209b, 211.
在製程室205中殘餘氣體的總壓力通常在約10-3毫巴和1000毫巴之間，其中相對高的、超過500毫巴或超過900毫巴的總壓力也是可能的。腔室205中的總壓力可以藉由壓力感測器(未圖示)進行監測，並且可以視情況地藉由控制裝置215以適當的控制閥207、209a、209b、211進行修改。 The total pressure of the residual gas in the process chamber 205 is typically between about 10 -3 mbar and 1000 mbar, with relatively high total pressures in excess of 500 mbar or over 900 mbar being possible. The total pressure in the chamber 205 can be monitored by a pressure sensor (not shown) and can optionally be modified by the control device 215 with appropriate control valves 207, 209a, 209b, 211.
氣態組分的檢測，更確切地說是測定各別檢測氣態組分的量或分壓，可被用於控制或調節沉積製程。舉例來說，在金屬有機前驅物或製程相關反應物(例如臭氧、摻雜氣體或殘餘氣體氛圍中的視情況金屬有機物及/或H2O)之濃度的基礎上，能夠識別淨化步驟何時可以完成(例如一旦各別的分壓落在預定臨界值以下時)。然後控制單元215(其具有到製程氣體分析器213a的訊號連接)可以在適當的時間打開或關閉各別的入口閥209a、209b或出口閥211，從而最佳化淨化步驟使用的持續時間。可以理解的是，類似地，最佳化上述兩個供應步驟的持續時間也是可能的。 The detection of gaseous components, and more specifically the determination of the amount or partial pressure of the respective gaseous components, can be used to control or condition the deposition process. For example, based on the concentration of metal organic precursors or process related reactants (eg, ozone, doping gas or optionally metal organics and/or H 2 O in a residual gas atmosphere), it is possible to identify when the purification step can Completed (eg, once the individual partial pressures fall below a predetermined threshold). The control unit 215, which has a signal connection to the process gas analyzer 213a, can then open or close the respective inlet valve 209a, 209b or outlet valve 211 at the appropriate time to optimize the duration of use of the purge step. It will be appreciated that similarly, it is also possible to optimize the duration of the two supply steps described above.
在質譜儀1的幫助下，不僅可以最佳化原子層沉積過程中的製程，而且還可以最佳化其它的塗佈製程，例如當在金屬有機化學氣相磊晶的情況下或在分子束磊晶的情況下進行(視情況以電漿輔助的)CVD製程、金屬有機CVD製程時，該等製程通常同樣地可以在來自圖1的(視情況稍微修改的)裝置1中進行。這同樣適用於基於物理氣相沉積的塗佈製程。在所有的這些情況下，可以在殘餘氣體氛圍中檢測到的氣體組分的基礎上以適當的方式採用或最佳化製程參數(溫度、壓力等)。 With the help of mass spectrometer 1, not only can the process in the atomic layer deposition process be optimized, but other coating processes can be optimized, for example in the case of metal organic chemical vapor epitaxy or in the molecular beam. In the case of epitaxial (in the case of plasma assisted) CVD processes, metal organic CVD processes, such processes are generally equally possible in the apparatus 1 (as modified from the case). The same applies to the coating process based on physical vapor deposition. In all of these cases, the process parameters (temperature, pressure, etc.) can be employed or optimized in an appropriate manner based on the gas composition detected in the residual gas atmosphere.
當質譜儀1被用在塗佈設備時，特別的是可以在質譜分析期間量測或檢測以下物質、其混合物及/或反應產物、團簇及/或化合物中之至少一者：H2、He、N2、O2、PH3、AsH3、B、P、As、CH4、CO、CO2、Ar、SCl4、SiHCl3、SiH2Cl2、H2O、CxHy、三甲基鎵、三乙基鎵、三甲基鋁、三乙基鋁、三甲基銦、三乙基銦、Cp2Mg、SiH4、Si2H6、四丁基銨、四丁基矽烷、Xe同位素、Kr同位素、六甲基二矽氧烷、叔丁基胂、三甲基胂、二乙基-叔丁基胂、二乙基-叔丁基膦、二-叔丁基膦、叔丁基肼、二甲基肼、 銦、鋁、鎵、硼、矽、金、銻、鉍。 When the mass spectrometer 1 is used in a coating apparatus, it is particularly possible to measure or detect at least one of the following substances, mixtures thereof and/or reaction products, clusters and/or compounds during mass spectrometry: H 2 , He, N 2 , O 2 , PH 3 , AsH 3 , B, P, As, CH 4 , CO, CO 2 , Ar, SCl 4 , SiHCl 3 , SiH 2 Cl 2 , H 2 O, C x H y , Trimethylgallium, triethylgallium, trimethylaluminum, triethylaluminum, trimethylindium, triethylindium, Cp 2 Mg, SiH 4 , Si 2 H 6 , tetrabutylammonium, tetrabutyl Decane, Xe isotope, Kr isotope, hexamethyldioxane, tert-butyl fluorene, trimethyl hydrazine, diethyl-tert-butyl fluorene, diethyl-tert-butylphosphine, di-tert-butylphosphine , tert-butyl fluorene, dimethyl hydrazine, indium, aluminum, gallium, boron, antimony, gold, antimony, bismuth.
該至少一種物質、混合物、反應產物、團簇及/或化合物特別是可以在15℃和5000℃之間的製程室205的溫度並在10-10毫巴和5巴之間的製程室205壓力下進行量測或檢測，該溫度較佳為在100℃和2000℃之間，該壓力較佳為在10-8毫巴和1巴之間。 The at least one substance, mixture, reaction product, cluster and/or compound, in particular, the temperature of the process chamber 205, which may be between 15 ° C and 5000 ° C, and the pressure of the process chamber 205 between 10 -10 mbar and 5 bar The measurement or detection is carried out, preferably at a temperature between 100 ° C and 2000 ° C, preferably between 10 -8 mbar and 1 bar.
特別的是，當在塗佈製程的過程中使用質譜儀1來分析(製程)氣體混合物時，若質譜儀1具有自清洗功能會是有利的，以去除沉積在量測室7或離子阱10中的製程氣體組分。用於實現這種原位自清洗的選擇被描述在WO 02/00962 A1中，其中清洗氣體被用來去除由製程氣體產生的沉積物。在圖1的質譜儀1中，可以在電漿源18中憑藉由氣體供應(此處未繪示)供應的清洗氣體來取代離子化氣體13而將清洗氣體轉化成電漿。離子化或激發的清洗氣體在與離子化氣體13相同的路徑上進入離子阱10中。視情況，清洗氣體也可以經由其他的氣體供應(此處未繪示)進入量測室7，並在量測室7中形成氣態的清洗產物與沉積物，該清洗產物可以被從離子阱10或從量測室7移出。 In particular, when the mass spectrometer 1 is used to analyze (process) the gas mixture during the coating process, it may be advantageous if the mass spectrometer 1 has a self-cleaning function to remove deposition in the measurement chamber 7 or the ion trap 10. Process gas composition in the process. The choice for achieving such in-situ self-cleaning is described in WO 02/00962 A1, in which a purge gas is used to remove deposits produced by process gases. In the mass spectrometer 1 of FIG. 1, the cleaning gas can be converted into a plasma by replacing the ionizing gas 13 with a cleaning gas supplied from a gas supply (not shown here) in the plasma source 18. The ionized or excited purge gas enters the ion trap 10 in the same path as the ionized gas 13. Optionally, the purge gas may also enter the measurement chamber 7 via other gas supplies (not shown) and form gaseous cleaning products and deposits in the measurement chamber 7, which may be from the ion trap 10 Or removed from the measuring chamber 7.
特別的是，若離子阱10被體現為電FT-ICR阱(其需要小的安裝空間)，則質譜儀1也可以被使用在安裝空間扮演著重要角色的應用中，例如被使用在MOCVD製程或類似的製程。 In particular, if the ion trap 10 is embodied as an electrical FT-ICR trap (which requires a small mounting space), the mass spectrometer 1 can also be used in applications where the mounting space plays an important role, for example in an MOCVD process. Or a similar process.
可以理解的是，由於上述的性質，質譜儀1也可以被用在其他的領域中，例如在其它的塗佈或蝕刻或植入製程中、在氣體分析中、在摻雜測試中、在法醫檢驗中等。 It can be understood that due to the above properties, the mass spectrometer 1 can also be used in other fields, such as in other coating or etching or implantation processes, in gas analysis, in doping tests, in forensics. The test is medium.
除了使用上述的質譜儀來進行氣體的質譜分析之外，也可以 將質譜儀使用在通常為機械振動的振動檢測或振動分析的領域中。特別的是，振動可以是設置或裝置的自然振動，將質譜儀安裝於該設置或裝置的內部，即在質譜儀的使用點檢測振動，而且質譜儀被用來作為振動感測器。為此目的，使用質譜儀來記錄待分析的振動頻率所在的頻率範圍內的頻譜。舉例來說，這種頻譜可以在約1Hz和約15kHz之間。複數個寄生頻率通常位在此頻率範圍內，該等寄生頻率是由機械振動產生的，而且可以藉由例如FT離子阱(特別是FT-ICR阱)的量測電極進行檢測和分析。舉例來說，為了分析振動，一旦質譜儀被安裝到裝置中即可記錄頻譜。假使該裝置在安裝的時候是處在良好的工作秩序中，則此頻譜可以作為參考頻譜。可以在稍後的時間或在幾個稍後的時間重複量測頻譜，並將測得的頻譜與參考頻譜進行比較。假使在測得的頻譜中檢測到一個或更多個另外的線或尖峰，則表示在裝置中的某處發生不良的振動，該不良的振動例如可被回溯到機械問題。舉例來說，振動可以是配置在質譜儀附近的滑動軸承或球軸承的不良自然振動，或由電源單元引起的振動(電源的嗡嗡聲)。舉例來說，在圖7繪示的塗佈設備201中，可以分析或檢測設置在質譜儀1附近的真空泵212(特別是該泵的滑動軸承或球軸承)的自然頻率f。 In addition to using the above mass spectrometer for mass spectrometry of gas, it is also possible The mass spectrometer is used in the field of vibration detection or vibration analysis, which is usually mechanical vibration. In particular, the vibration can be the natural vibration of the setup or device, the mass spectrometer being mounted inside the setup or device, ie the vibration is detected at the point of use of the mass spectrometer, and the mass spectrometer is used as a vibration sensor. For this purpose, a mass spectrometer is used to record the frequency spectrum in the frequency range in which the vibration frequency to be analyzed lies. For example, such a spectrum can be between about 1 Hz and about 15 kHz. A plurality of spurious frequencies are typically located in this frequency range, which are generated by mechanical vibration and can be detected and analyzed by a measuring electrode such as an FT ion trap (especially an FT-ICR trap). For example, to analyze vibration, the spectrum can be recorded once the mass spectrometer is installed in the device. This spectrum can be used as a reference spectrum if the device is in good working order at the time of installation. The spectrum can be measured at a later time or at a later time, and the measured spectrum is compared to the reference spectrum. If one or more additional lines or spikes are detected in the measured spectrum, it indicates that a bad vibration has occurred somewhere in the device, which can be traced back to mechanical problems, for example. For example, the vibration may be a poor natural vibration of a sliding bearing or a ball bearing disposed near the mass spectrometer, or a vibration caused by a power supply unit (a click of a power source). For example, in the coating apparatus 201 illustrated in FIG. 7, the natural frequency f of the vacuum pump 212 (particularly the sliding bearing or ball bearing of the pump) disposed near the mass spectrometer 1 can be analyzed or detected.
1‧‧‧質譜儀 1‧‧‧Mass Spectrometer
2‧‧‧氣體混合物 2‧‧‧ gas mixture
2a‧‧‧氣體脈衝 2a‧‧‧ gas pulse
3a‧‧‧物質 3a‧‧‧ Substance
3b‧‧‧粒子 3b‧‧‧ particles
3a、3b‧‧‧離子化組分 3a, 3b‧‧‧ ionized components
4‧‧‧出口 4‧‧‧Export
5‧‧‧可控閥 5‧‧‧Controllable valve
6‧‧‧入口 6‧‧‧ entrance
7‧‧‧量測室 7‧‧‧Measurement room
8‧‧‧腔室 8‧‧‧ chamber
10‧‧‧離子阱 10‧‧‧Ion trap
11‧‧‧壓力降低單元 11‧‧‧pressure reduction unit
11a‧‧‧模組化壓力階段 11a‧‧‧Modular pressure stage
11b‧‧‧模組化壓力階段 11b‧‧‧Modular pressure stage
11c‧‧‧模組化壓力階段 11c‧‧‧Modular pressure stage
12‧‧‧離子化裝置 12‧‧‧Ionization device
13‧‧‧離子化氣體 13‧‧‧Ionized gas
13a‧‧‧離子 13a‧‧‧ ions
13b‧‧‧介穩態粒子 13b‧‧‧Mesogenic particles
14‧‧‧殘餘氣體 14‧‧‧Residual gas
14a‧‧‧離子 14a‧‧‧ ions
15‧‧‧計量閥 15‧‧‧ metering valve
16‧‧‧氣體供應管線 16‧‧‧ gas supply pipeline
17‧‧‧氣體貯槽 17‧‧‧ gas storage tank
18‧‧‧電漿源 18‧‧‧ Plasma source
19‧‧‧控制裝置 19‧‧‧Control device
Claims (30)
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE201310213501 DE102013213501A1 (en) | 2013-07-10 | 2013-07-10 | Mass spectrometer, its use, and method for mass spectrometric analysis of a gas mixture |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| TW201503217A TW201503217A (en) | 2015-01-16 |
| TWI579888B true TWI579888B (en) | 2017-04-21 |
Family
ID=50156760
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| TW103105973A TWI579888B (en) | 2013-07-10 | 2014-02-21 | Mass spectrometer, the use thereof, and methods for mass spectrometric analysis of gas mixtures |
Country Status (7)
| Country | Link |
|---|---|
| US (1) | US10304672B2 (en) |
| EP (1) | EP3020063A1 (en) |
| JP (1) | JP6535660B2 (en) |
| KR (1) | KR102219556B1 (en) |
| DE (1) | DE102013213501A1 (en) |
| TW (1) | TWI579888B (en) |
| WO (1) | WO2015003819A1 (en) |
Families Citing this family (19)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| NL2016199A (en) * | 2015-03-03 | 2016-09-30 | Asml Netherlands Bv | Radiation Sensor Apparatus. |
| DE102015208188A1 (en) | 2015-05-04 | 2016-11-24 | Carl Zeiss Smt Gmbh | Method for mass spectrometric analysis of a gas and mass spectrometer |
| CN104882352B (en) * | 2015-05-18 | 2017-04-05 | 中国计量科学研究院 | The mass spectrometric apparatus and analysis method of ion molecule reaction |
| KR101780398B1 (en) * | 2016-01-13 | 2017-10-11 | 서울대학교산학협력단 | Apparatus and method for producing inert gas negative ion |
| EP3316278A1 (en) * | 2016-10-26 | 2018-05-02 | NovionX UG (haftungsbeschränkt) | Verfahren zur spektrometrie |
| KR20190119106A (en) | 2017-02-21 | 2019-10-21 | 칼 짜이스 에스엠티 게엠베하 | Real-time monitoring method of process and mass spectrometer |
| DE102017208996B4 (en) | 2017-05-29 | 2024-05-08 | Leybold Gmbh | Method for mass spectrometric analysis of a gas |
| JP6344783B1 (en) * | 2017-06-21 | 2018-06-20 | エフビートライアングル株式会社 | Evaluation system based on gas analysis |
| GB201802917D0 (en) | 2018-02-22 | 2018-04-11 | Micromass Ltd | Charge detection mass spectrometry |
| JP6779469B2 (en) * | 2018-03-27 | 2020-11-04 | 信越半導体株式会社 | Sample analysis method, sample introduction device |
| DE102018216623A1 (en) | 2018-09-27 | 2020-04-02 | Carl Zeiss Smt Gmbh | Mass spectrometer and method for mass spectrometric analysis of a gas |
| DE102019204694A1 (en) * | 2019-04-02 | 2020-10-08 | Carl Zeiss Smt Gmbh | Mass spectrometer with an ionization device |
| US11502160B2 (en) | 2020-03-02 | 2022-11-15 | Taiwan Semiconductor Manufacturing Co., Ltd. | Method and system for forming metal-insulator-metal capacitors |
| US11842891B2 (en) | 2020-04-09 | 2023-12-12 | Waters Technologies Corporation | Ion detector |
| DE102020209157A1 (en) | 2020-07-21 | 2022-01-27 | Carl Zeiss Smt Gmbh | Residual gas analyzer and EUV lithography system with a residual gas analyzer |
| KR102450029B1 (en) * | 2020-11-06 | 2022-10-05 | 한국과학기술연구원 | Mass Spectrum Analysis Method |
| CN113862641B (en) * | 2021-08-16 | 2023-09-12 | 江汉大学 | Monitoring system for atomic layer deposition precursor dosage, method and application thereof |
| GB2612580A (en) * | 2021-10-29 | 2023-05-10 | Thermo Fisher Scient Bremen Gmbh | Method for determining a measure of a rate of decay and mass spectrometry system |
| DE102022204996A1 (en) | 2022-05-19 | 2023-11-23 | Carl Zeiss Smt Gmbh | Method and device for determining a residual gas using a residual gas analysis method in a vacuum of a vacuum chamber |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0575777A2 (en) * | 1992-05-29 | 1993-12-29 | Varian Associates, Inc. | Methods of using ion trap mass spectrometers |
| US7095019B1 (en) * | 2003-05-30 | 2006-08-22 | Chem-Space Associates, Inc. | Remote reagent chemical ionization source |
| TWI271771B (en) * | 2006-01-27 | 2007-01-21 | Univ Nat Sun Yat Sen | Electrospray-assisted laser desorption ionization devices, mass spectrometers, and methods for mass spectrometry |
| TW200937487A (en) * | 2007-10-10 | 2009-09-01 | Mks Instr Inc | Chemical ionization reaction or proton transfer reaction mass spectrometry with a quadrupole or time-of-flight mass spectrometer |
| DE102008041592A1 (en) * | 2008-08-27 | 2010-03-04 | Carl Zeiss Smt Ag | Detection of contaminants in an EUV lithography system |
| US8178833B2 (en) * | 2007-06-02 | 2012-05-15 | Chem-Space Associates, Inc | High-flow tube for sampling ions from an atmospheric pressure ion source |
Family Cites Families (23)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5107109A (en) * | 1986-03-07 | 1992-04-21 | Finnigan Corporation | Method of increasing the dynamic range and sensitivity of a quadrupole ion trap mass spectrometer |
| US5572022A (en) * | 1995-03-03 | 1996-11-05 | Finnigan Corporation | Method and apparatus of increasing dynamic range and sensitivity of a mass spectrometer |
| US5625184A (en) * | 1995-05-19 | 1997-04-29 | Perseptive Biosystems, Inc. | Time-of-flight mass spectrometry analysis of biomolecules |
| DE19930894B4 (en) | 1999-07-05 | 2007-02-08 | Bruker Daltonik Gmbh | Method for controlling the number of ions in ion cyclotron resonance mass spectrometers |
| WO2002000962A1 (en) | 2000-06-28 | 2002-01-03 | Mks Instruments, Inc. | System and method for in-situ cleaning of process monitor of semi-conductor wafer fabricator |
| CA2652064C (en) * | 2001-05-25 | 2010-10-05 | Analytica Of Branford, Inc. | Multiple detection systems |
| US8110814B2 (en) | 2003-10-16 | 2012-02-07 | Alis Corporation | Ion sources, systems and methods |
| US7189967B1 (en) * | 2004-06-16 | 2007-03-13 | Analytica Of Branford, Inc. | Mass spectrometry with multipole ion guides |
| GB0416288D0 (en) * | 2004-07-21 | 2004-08-25 | Micromass Ltd | Mass spectrometer |
| GB2427067B (en) * | 2005-03-29 | 2010-02-24 | Thermo Finnigan Llc | Improvements relating to ion trapping |
| CA2621126C (en) * | 2005-09-15 | 2011-04-12 | Phenomenome Discoveries Inc. | Method and apparatus for fourier transform ion cyclotron resonance mass spectrometry |
| WO2007067296A2 (en) * | 2005-12-02 | 2007-06-14 | Alis Corporation | Ion sources, systems and methods |
| US7465919B1 (en) | 2006-03-22 | 2008-12-16 | Itt Manufacturing Enterprises, Inc. | Ion detection system with neutral noise suppression |
| US20070224697A1 (en) * | 2006-03-24 | 2007-09-27 | Bruker Daltonics, Inc. | Means and method for analyzing samples by mass spectrometry |
| GB0607542D0 (en) * | 2006-04-13 | 2006-05-24 | Thermo Finnigan Llc | Mass spectrometer |
| TWI484529B (en) | 2006-11-13 | 2015-05-11 | Mks Instr Inc | Ion trap mass spectrometer, method of obtaining mass spectrum using the same, ion trap, method of and apparatus for trapping ions in ion trap |
| GB0820308D0 (en) | 2008-11-06 | 2008-12-17 | Micromass Ltd | Mass spectrometer |
| US9202678B2 (en) * | 2008-11-14 | 2015-12-01 | Board Of Trustees Of Michigan State University | Ultrafast laser system for biological mass spectrometry |
| KR101570652B1 (en) * | 2009-05-06 | 2015-11-23 | 엠케이에스 인스트루먼츠, 인코포레이티드 | Electrostatic ion trap |
| JP5406621B2 (en) | 2009-08-06 | 2014-02-05 | 勝 堀 | Sample substrate for laser desorption / ionization mass spectrometry, laser desorption / ionization mass spectrometry method and apparatus using the same |
| JP5600430B2 (en) * | 2009-12-28 | 2014-10-01 | 株式会社日立ハイテクノロジーズ | Mass spectrometer and mass spectrometry method |
| US8785845B2 (en) * | 2010-02-02 | 2014-07-22 | Dh Technologies Development Pte. Ltd. | Method and system for operating a time of flight mass spectrometer detection system |
| CN102169791B (en) * | 2010-02-05 | 2015-11-25 | 岛津分析技术研发（上海）有限公司 | A kind of cascade mass spectrometry device and mass spectrometric analysis method |
-
2013
- 2013-07-10 DE DE201310213501 patent/DE102013213501A1/en not_active Ceased
-
2014
- 2014-02-20 KR KR1020167001270A patent/KR102219556B1/en active IP Right Grant
- 2014-02-20 WO PCT/EP2014/053361 patent/WO2015003819A1/en active Application Filing
- 2014-02-20 JP JP2016524707A patent/JP6535660B2/en not_active Expired - Fee Related
- 2014-02-20 EP EP14706019.8A patent/EP3020063A1/en not_active Ceased
- 2014-02-21 TW TW103105973A patent/TWI579888B/en not_active IP Right Cessation
-
2015
- 2015-12-14 US US14/967,699 patent/US10304672B2/en not_active Expired - Fee Related
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0575777A2 (en) * | 1992-05-29 | 1993-12-29 | Varian Associates, Inc. | Methods of using ion trap mass spectrometers |
| US7095019B1 (en) * | 2003-05-30 | 2006-08-22 | Chem-Space Associates, Inc. | Remote reagent chemical ionization source |
| TWI271771B (en) * | 2006-01-27 | 2007-01-21 | Univ Nat Sun Yat Sen | Electrospray-assisted laser desorption ionization devices, mass spectrometers, and methods for mass spectrometry |
| US8178833B2 (en) * | 2007-06-02 | 2012-05-15 | Chem-Space Associates, Inc | High-flow tube for sampling ions from an atmospheric pressure ion source |
| TW200937487A (en) * | 2007-10-10 | 2009-09-01 | Mks Instr Inc | Chemical ionization reaction or proton transfer reaction mass spectrometry with a quadrupole or time-of-flight mass spectrometer |
| DE102008041592A1 (en) * | 2008-08-27 | 2010-03-04 | Carl Zeiss Smt Ag | Detection of contaminants in an EUV lithography system |
Also Published As
| Publication number | Publication date |
|---|---|
| KR20160030186A (en) | 2016-03-16 |
| US20160111269A1 (en) | 2016-04-21 |
| TW201503217A (en) | 2015-01-16 |
| WO2015003819A1 (en) | 2015-01-15 |
| KR102219556B1 (en) | 2021-02-24 |
| US10304672B2 (en) | 2019-05-28 |
| JP2016530502A (en) | 2016-09-29 |
| DE102013213501A1 (en) | 2015-01-15 |
| EP3020063A1 (en) | 2016-05-18 |
| JP6535660B2 (en) | 2019-06-26 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| TWI579888B (en) | Mass spectrometer, the use thereof, and methods for mass spectrometric analysis of gas mixtures | |
| JP6663407B2 (en) | Method and mass spectrometer for mass spectrometric testing of gas mixtures | |
| US20140299577A1 (en) | Apparatus and method for surface processing of a substrate | |
| US5087815A (en) | High resolution mass spectrometry of recoiled ions for isotopic and trace elemental analysis | |
| US7153362B2 (en) | System and method for real time deposition process control based on resulting product detection | |
| US7355171B2 (en) | Method and apparatus for process monitoring and control | |
| Donnelly et al. | Critical review: Plasma-surface reactions and the spinning wall method | |
| US11791147B2 (en) | Mass spectrometer and method for analysing a gas by mass spectrometry | |
| US20110210243A1 (en) | Metastable CID | |
| US5397895A (en) | Photoionization mass spectroscopy flux monitor | |
| Yasumatsu et al. | Ultrahigh-sensitive detection of molecules produced in catalytic reactions by uni-atomic-composition bi-element clusters supported on solid substrate | |
| Fachinger et al. | The ion trap aerosol mass spectrometer: field intercomparison with the ToF-AMS and the capability of differentiating organic compound classes via MS-MS | |
| WO2023074480A1 (en) | Gas analysis device and control method | |
| Fuke | Preparation of ultracold ions in strong magnetic field and application to gas-phase NMR spectroscopy II | |
| JP7343944B2 (en) | Gas analyzer and control method | |
| Johnsen | Recombination of cluster ions | |
| CN113169028B (en) | Mass spectrometer and method for analysing a gas by mass spectrometry | |
| De Urquijo et al. | Drift and proton transfer reactions of positive ions in methane parent gas | |
| Gasc et al. | Novel Time-of-Flight Residual Gas Analyzer (TOF-RGA) for in situ Real-time Process Monitoring | |
| KR20240088888A (en) | Gas analysis device and control method | |
| JPH0581858B2 (en) | ||
| Pontoh | ECR plasma analysis: correlation between plasma conditions and growth rate | |
| JPH08315767A (en) | Trace gas analyzer | |
| Guha | Study of the plasma surface interactions by the “spinning wall” technique |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| MM4A | Annulment or lapse of patent due to non-payment of fees |